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Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S1
Supporting Information for
Probing Trends in Enantioinduction via Substrate Design: Palladium-
Catalyzed Decarboxylative Allylic Alkylation of a-Enaminones
Douglas C. Duquette, Alexander Q. Cusumano, Louise Lefoulon, Jared T. Moore, and Brian M.
Stoltz*
Warren and Katharine Schlinger Laboratory of Chemistry and Chemical Engineering, Division
of Chemistry and Chemical Engineering, California Institute of Technology, MC 101-20,
Pasadena, California 91125, United States
Table of Contents:
Materials and Methods ................................................................................................................................................. S2
List of Abbreviations .................................................................................................................................................... S3
General Procedure for Pd-Catalyzed Allylic Alkylation Reactions ............................................................................ S4
Determination of Enantiomeric Excess ..................................................................................................................... S13
Synthesis of Allylic Alkylation Substrates ................................................................................................................ S16
Derivatization of Enaminone Products ...................................................................................................................... S27
References ................................................................................................................................................................. S32
NMR and IR Spectra of New Compounds ................................................................................................................ S33
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S2
Materials and Methods
Unless otherwise stated, reactions were performed in flame-dried glassware under an argon
or nitrogen atmosphere using dry, deoxygenated solvents. Reactions were heated by pre-heated oil
bath unless otherwise specified. Solvents were dried by passage through an activated alumina
column under argon.1 Acetone was used directly from a Sigma-Aldrich ACS reagent grade bottle.
Brine solutions are saturated aqueous solutions of sodium chloride. Reagents were purchased from
Sigma-Aldrich, Acros Organics, Strem, or Alfa Aesar and used as received unless otherwise stated.
The (S)-t-BuPHOX (L1) ligand was prepared by known methods.2 Reaction progress was
monitored by thin-layer chromatography (TLC) or Agilent 1290 UHPLC-MS. TLC was performed
using E. Merck silica gel 60 F254 precoated glass plates (0.25 mm) and visualized by UV
fluorescence quenching or KMnO4 staining. Silicycle SiliaFlash® P60 Academic Silica gel
(particle size 40–63 nm) was used for flash column chromatography. 1H NMR spectra were
recorded on Varian Inova 500 MHz, Varian 400 MHz, and Bruker 400 MHz spectrometers and
are reported relative to residual CHCl3 (δ 7.26 ppm). 13C NMR spectra were recorded on a Varian
Inova 500 MHz spectrometer (125 MHz), a Varian 400 MHz spectrometer (100 MHz), and Bruker
400 MHz spectrometers (100 MHz) and are reported relative to CHCl3 (δ 77.16 ppm). Data for 1H
NMR are reported as follows: chemical shift (δ ppm) (multiplicity, coupling constant (Hz),
integration). Multiplicities are reported as follows: s = singlet, d = doublet, t = triplet, q = quartet,
p = pentet, sept = septuplet, m = multiplet, dm = doublet of multiplets, br s = broad singlet, br d =
broad doublet, app = apparent. Data from 13C NMR spectra are reported in terms of chemical
shifts (δ ppm). IR spectra were obtained by use of a Perkin Elmer Spectrum BXII spectrometer
using thin films deposited on NaCl plates and reported in frequency of absorption (cm-1). Optical
rotations were measured with a Jasco P-2000 polarimeter operating on the sodium D-line (589
nm), using a 100 mm path-length cell and are reported as: [α]D25 (concentration in g/100 mL,
solvent, ee). Analytical chiral HPLC was performed with an Agilent 1100 Series HPLC utilizing
a Chiralpak (AD, AD- H, or AS) or Chiralcel (OD-H, OJ-H, or OB-H) columns (4.6 mm x 25 cm)
obtained from Daicel Chemical Industries, Ltd. Analytical chiral SFC was performed with a
Mettler SFC supercritical CO2 analytical chromatography system with Chiralpak AD-H column,
OD-H column, and OJ-H column obtained from Daicel Chemical Industries, Ltd. High resolution
mass spectra (HRMS) were obtained from the Caltech Mass Spectral Facility (GC-EI+, EI+, or
FAB+) or Agilent 6200 Series TOF with an Agilent G1978A Multimode source in electrospray
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
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ionization (ESI+), atmospheric pressure chemical ionization (APCI+), or mixed ionization mode
(MM: ESI-APCI+).
List of Abbreviations:
ee – enantiomeric excess, SFC – supercritical fluid chromatography, TLC – thin-layer
chromatography, IPA – isopropanol, NBS – N-bromosuccinimide,
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
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General Procedure A: Palladium-Catalyzed Allylic Alkylation Reactions
In a glove box under an atmosphere of N2, Pd2(dmdba)3 (29.7 mg, 23.3 µmol, 5 mol %) and (S)-t-
BuPHOX ligand (22.5 mg, 58.2 µmol, 12.5 mol %) were dissolved in EtOAc (12 mL). The catalyst
mixture was let stir at 40 ºC in a pre-heated vial block for 30 minutes. At this point, a solution of
allyl b-ketoester (1, 130 mg, 0.465 mmol, 1.00 equiv) in EtOAc (2.0 mL, final concentration of
0.033 M with respected to 1) was added. The reaction mixture was sealed, removed from the glove
box and stirred at 40 °C in a pre-heated vial block until the reaction was complete as indicated by
TLC analysis (typically around 9-12 hours). The reaction mixture was filtered through a short plug
of silica, being eluted with additional EtOAc (25 mL). The filtrate was concentrated in vacuo and
purified by flash column chromatography to afford the desired enaminone product 2.
Note: After pre-complexation of catalyst the reaction mixture is red/brown in color, which changes
immediately to light green upon addition of substrate. Upon completion, the reaction returns to
the original red/brown color.
(S)-6-allyl-6-methyl-2-morpholinocyclohex-2-en-1-one (2a)
Prepared according to general procedure A using substrate 1a. The product was purified by flash
column chromatography (SiO2, 5–10% acetone in hexanes) to yield enaminone 2a as a colorless
oil (104 mg, 0.442 mmol, 95% yield). Rf = 0.22 (20% acetone in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.88 (t, J = 4.5 Hz, 1H), 5.78 – 5.69 (m, 1H), 5.06 – 5.02 (m, 2H), 3.80 (ddd, J = 5.7,
3.5, 2.2 Hz, 4H), 2.82 (dt, J = 9.9, 4.6 Hz, 2H), 2.73 – 2.67 (m, 2H), 2.48 – 2.38 (m, 2H), 2.34
(ddd, J = 13.8, 7.2, 1.1 Hz, 1H), 2.23 (dd, J = 13.7, 7.7 Hz, 1H), 1.88 (dt, J = 13.8, 6.0 Hz, 1H),
1.73 (ddd, J = 13.9, 6.9, 5.7 Hz, 1H), 1.09 (s, 3H).; 13C NMR (125 MHz, CDCl3) δ 200.4, 145.5,
134.0, 125.0, 118.1, 66.9, 50.5, 45.4, 41.2, 33.2, 21.9, 21.8; IR (Neat Film, NaCl): 2960, 2918,
O
OR1
O Pd2(dmdba)3 (5 mol%)
EtOAc, 40 ºC, 9 h
OR1N N
OO
(S)–2(±)–1
R2R2
(S)-t-BuPHOX (12.5 mol%)
OMe
NO
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S5
2853, 2813, 1679, 1615, 1447, 1376, 1262, 1208, 1120, 1099, 1001, 990, 915 cm-1; HRMS (ESI-
APCI) m/z: [M+H]+ Calc’d for C14H22NO2 236.1645; Found 236.1641; [α]25 –315.66 (c 13.57,
CHCl3, 99% ee).
(S)-6-allyl-6-ethyl-2-morpholinocyclohex-2-en-1-one (2b)
Prepared according to general procedure A using substrate 1b. The product was purified by flash
column chromatography (SiO2, 5–10% acetone in hexanes) to yield enaminone 2b as a colorless
oil (116 mg, 0.465 mmol, 99% yield). Rf = 0.25 (40% Et2O in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.83 (t, J = 4.4 Hz, 1H), 5.73 – 5.66 (m, 1H), 5.04 – 5.02 (m, 1H), 5.01 – 4.99 (m, 1H),
3.79 – 3.77 (m, 4H), 2.80 – 2.74 (m, 2H), 2.70 (ddd, J = 11.6, 7.4, 4.2 Hz, 2H), 2.40 (tdd, J = 5.9,
4.5, 1.4 Hz, 2H), 2.34 (ddt, J = 14.0, 6.9, 1.3 Hz, 1H), 2.23 (ddt, J = 14.0, 7.9, 1.1 Hz, 1H), 1.81
(t, J = 6.2 Hz, 2H), 1.59 (qd, J = 7.5, 1.3 Hz, 2H), 0.80 (t, J = 7.5 Hz, 3H).; 13C NMR (125 MHz,
CDCl3) δ 200.2, 146.0, 134.4, 124.8, 117.9, 67.0, 50.6, 48.6, 38.8, 30.4, 27.0, 21.8, 8.4; IR (Neat
Film, NaCl): 2962, 2933, 2854, 2814, 1678, 1616, 1447, 1377, 1263, 1208, 1120, 1070, 1099, 998
cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C15H24NO2 250.1802; Found 250.1813; [α]25
5.52 (c 7.45, CHCl3, 98% ee).
(S)-6-allyl-6-(((tert-butyldimethylsilyl)oxy)methyl)-2-morpholinocyclohex-2-en-1-one (2c)
Prepared according to general procedure A using substrate 1c. The product was purified by flash
column chromatography (SiO2, 20% acetone in hexanes) to yield enaminone 2c (164 mg, 0.445
mmol, 96% yield) as a pale tan oil; Rf = 0.33 (20% EtOAc in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.87 (t, J = 4.6 Hz, 1H), 5.74 – 5.66 (m, 1H), 5.04 – 5.00 (m, 2H), 3.78 (t, J = 4.6 Hz,
4H), 3.68 (d, J = 9.7 Hz, 1H), 3.62 (d, J = 9.7 Hz, 1H), 2.74 (t, J = 4.7 Hz, 4H), 2.43 – 2.38 (m,
3H), 2.26 (ddt, J = 13.8, 7.8, 1.1 Hz, 1H), 1.96 (ddd, J = 13.3, 7.1, 6.0 Hz, 1H), 1.89 (dt, J = 13.7,
5.9 Hz, 1H), 0.85 (s, 9H), 0.01 (s, 3H), 0.01 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 198.8, 146.4,
134.1, 125.1, 118.0, 67.0, 66.1, 51.0, 50.5, 37.2, 28.5, 26.0, 21.7, 18.3, -5.4, -5.5; IR (Neat Film,
OEt
NO
ON
O OTBS
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S6
NaCl): 2953, 2855, 1677, 1639, 1615, 1472, 1463, 1447, 1378, 1299, 1262, 1208, 1121, 973, 917
cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C20H36NO3Si 366.2459; Found 366.2466; [α]25
–111.67 (c 10.25, CHCl3, 99% ee).
(S)-6-allyl-6-(2-((tert-butyldimethylsilyl)oxy)ethyl)-2-morpholinocyclohex-2-en-1-one (2d)
Prepared according to general procedure A using substrate 1d. The product was purified by flash
column chromatography (SiO2, 20% acetone in hexanes) to yield enaminone 2d (165 mg, 0.432
mmol, 93% yield) as a colorless oil; Rf = 0.31 (20% EtOAc in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.87 (s, 1H), 5.74 (dddd, J = 16.5, 10.5, 7.8, 6.9 Hz, 1H), 5.08 – 5.01 (m, 2H), 3.85 –
3.76 (m, 4H), 3.70 (ddd, J = 10.2, 8.4, 6.1 Hz, 1H), 3.57 (ddd, J = 10.3, 8.6, 5.9 Hz, 1H), 2.82 –
2.68 (m, 4H), 2.51 – 2.35 (m, 3H), 2.27 (dd, J = 14.0, 7.8 Hz, 1H), 1.92 – 1.82 (m, 3H), 1.75 (ddd,
J = 14.0, 8.4, 5.9 Hz, 1H), 0.87 (s, 9H), 0.03 (s, 3H), 0.02 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
199.6, 145.8, 134.2, 125.0, 118.3, 67.0, 59.5, 50.6, 47.8, 39.5, 37.0, 31.3, 26.1, 21.9, 18.4, -5.1, -
5.2; IR (Neat Film, NaCl): 2953, 2928, 2855, 2817, 1679, 1616, 1448, 1262, 1207, 1121, 1098,
1030, 977, 914 cm-1; HRMS (APCI) m/z: [M+H]+ calc’d for C21H38NO3Si 380.2615; Found
380.2618; [α]25 –9.38 (c 3.48, CHCl3, 99% ee).
Methyl (R)-3-(1-allyl-3-morpholino-2-oxocyclohex-3-en-1-yl)propanoate (2e)
Prepared according to general procedure A using substrate 1e. The product was purified by flash
column chromatography (SiO2, 5–50% EtOAc in hexanes) to yield enaminone 2e (140 mg, 0.456
mmol, 98% yield) as a colorless oil; Rf = 0.31 (20% EtOAc in hexanes); Rf = 0.40 (50% EtOAc in
hexanes); 1H NMR (500 MHz, CDCl3) δ 5.86 (t, J = 4.4 Hz, 1H), 5.73 – 5.65 (m, 1H), 5.07 – 5.02
(m, 2H), 3.77 (td, J = 4.8, 1.1 Hz, 4H), 3.63 (s, 3H), 2.77 – 2.70 (m, 4H), 2.43 (td, J = 5.9, 4.1 Hz,
2H), 2.35 – 2.28 (m, 2H), 2.26 – 2.16 (m, 2H), 1.93 (dddd, J = 14.1, 11.2, 5.4, 1.0 Hz, 1H), 1.86 –
ON
OOTBS
ON
OCO2Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S7
1.80 (m, 3H); 13C NMR (125 MHz, CDCl3) δ 199.1, 174.0, 145.7, 133.3, 125.0, 118.6, 66.8, 51.6,
50.4, 47.8, 38.9, 30.6, 29.2, 28.8, 21.6; IR (Neat Film, NaCl): 2950, 2853, 1735, 1676, 1617, 1437,
1375, 1263, 1207, 1174, 1119 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C17H26NO4
308.1856; Found 308.1859; [α]25 34.36 (c 16.49, CHCl3, 97% ee).
(R)-6-allyl-2-morpholino-6-(3-oxobutyl)cyclohex-2-en-1-one (2f)
Prepared according to general procedure A using substrate 1f. The product was purified by flash
column chromatography (SiO2, 20–50% EtOAc in hexanes) to yield enaminone 2f (122 mg, 0.419
mmol, 90% yield) as a colorless oil; Rf = 0.35 (50% EtOAc in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.89 (t, J = 4.5 Hz, 1H), 5.69 (ddt, J = 16.6, 10.4, 7.3 Hz, 1H), 5.08 – 5.03 (m, 2H), 3.79
(t, J = 4.7 Hz, 4H), 2.78 (dt, J = 11.6, 4.7 Hz, 2H), 2.70 (dt, J = 11.5, 4.7 Hz, 2H), 2.50 – 2.43 (m,
3H), 2.32 (tdd, J = 9.5, 6.7, 3.9 Hz, 2H), 2.25 (ddt, J = 14.0, 7.6, 1.2 Hz, 1H), 2.12 (s, 3H), 1.89 –
1.75 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 208.6, 199.6, 145.9, 133.6, 118.7, 67.0, 50.7, 47.9,
39.3, 38.4, 31.0, 30.2, 30.2, 28.0, 21.8; IR (Neat Film, NaCl): 2921, 2853, 2814, 1716, 1674, 1615,
1446, 1369, 1262, 1206, 1167, 1119, 978, 922 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for
C17H26NO3 292.1907; Found 292.1914; [α]25 15.98 (c 10.28, CHCl3, 94% ee).
(R)-3-(1-allyl-3-morpholino-2-oxocyclohex-3-en-1-yl)propanenitrile (2g)
Prepared according to general procedure A using substrate 1g. The product was purified by flash
column chromatography (SiO2, 5–50% EtOAc in hexanes) to yield enaminone 2g (217 mg, 0.465
mmol, 99% yield) as a colorless oil; Rf = 0.30 (50% EtOAc in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.90 (t, J = 4.5 Hz, 1H), 5.64 (ddt, J = 17.4, 10.1, 7.4 Hz, 1H), 5.13 – 5.06 (m, 2H), 3.81
– 3.74 (m, 4H), 2.82 (ddd, J = 11.7, 5.3, 3.4 Hz, 2H), 2.65 (ddd, J = 11.6, 5.9, 3.4 Hz, 2H), 2.54 –
2.24 (m, 6H), 2.07 (ddd, J = 14.0, 10.2, 5.9 Hz, 1H), 1.92 – 1.83 (m, 2H), 1.78 (ddd, J = 14.1, 10.2,
ON
O
MeO
ON
OCN
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S8
5.8 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 198.5, 145.7, 132.4, 125.4, 120.1, 119.5, 77.4, 77.2,
76.9, 66.9, 50.5, 48.0, 48.0, 38.8, 30.5, 30.3, 21.6, 12.3; IR (Neat Film, NaCl): 2929, 2854, 1675,
1448, 1263, 1205, 1118, 1000, 924 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C16H23N2O2
275.1754; Found 275.1753; [α]25 29.26 (c 11.02, CHCl3, 94% ee).
(S)-6-allyl-6-benzyl-2-morpholinocyclohex-2-en-1-one (2h)
Prepared according to general procedure A using substrate 1h. The product was purified by flash
column chromatography (SiO2, 5–20% acetone in hexanes) to yield enaminone 2h (217 mg, 0.442
mmol, 95% yield) as a colorless oil; Rf = 0.20 (40% Et2O in hexanes; 1H NMR (500 MHz, CDCl3)
δ 7.25 – 7.17 (m, 3H), 7.15 – 7.09 (m, 2H), 5.88 (t, J = 4.5 Hz, 1H), 5.77 (dddd, J = 16.9, 10.2,
8.0, 6.6 Hz, 1H), 5.11 – 5.02 (m, 2H), 3.80 (dd, J = 5.2, 4.2 Hz, 4H), 3.07 (d, J = 13.5 Hz, 1H),
2.80 – 2.70 (m, 5H), 2.47 – 2.39 (m, 3H), 2.15 (ddt, J = 14.0, 8.0, 1.1 Hz, 1H), 1.80 (dt, J = 13.9,
5.8 Hz, 1H), 1.75 – 1.69 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 199.2, 146.3, 137.6, 134.1, 130.9,
128.1, 126.5, 125.2, 118.6, 67.0, 50.6, 49.9, 40.7, 39.8, 29.8, 21.9; IR (Neat Film, NaCl): 2919,
2854, 2814, 1675, 1614, 1447, 1263, 1205, 1119, 981, 923 cm-1; HRMS (ESI-APCI) m/z: [M+H]+
calc’d for C20H26NO2 312.1958; Found 312.1967; [α]25 –95.78 (c 4.69, CHCl3, 96% ee).
(S)-6-allyl-6-(4-methoxybenzyl)-2-morpholinocyclohex-2-en-1-one (2i)
Prepared according to general procedure A using substrate 1i. The product was purified by flash
column chromatography (SiO2, 5–20% acetone in hexanes) to yield enaminone 2i (159 mg, 0.465
mmol, 99% yield) as a colorless oil; Rf = 0.17 (40% Et2O in hexanes); 1H NMR (500 MHz, CDCl3)
δ 7.05 – 7.02 (m, 2H), 6.79 – 6.76 (m, 2H), 5.87 (t, J = 4.5 Hz, 1H), 5.76 (dddd, J = 16.8, 10.2,
8.0, 6.6 Hz, 1H), 5.09 – 5.01 (m, 2H), 3.80 (t, J = 4.7 Hz, 4H), 3.77 (s, 3H), 3.01 (d, J = 13.8 Hz,
1H), 2.75 (q, J = 4.9 Hz, 4H), 2.66 (d, J = 13.8 Hz, 1H), 2.45 – 2.40 (m, 3H), 2.13 (ddt, J = 13.9,
8.0, 1.1 Hz, 1H), 1.80 (dt, J = 13.8, 5.9 Hz, 1H), 1.71 (dt, J = 13.9, 6.5 Hz, 1H); 13C NMR (125
OBn
NO
ON
OOMe
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
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MHz, CDCl3) δ 199.3, 158.3, 146.3, 134.1, 131.8, 129.5, 125.3, 118.5, 113.5, 67.0, 55.3, 55.2,
50.6, 50.0, 39.9, 39.8, 29.7, 21.9; IR (Neat Film, NaCl): 2930, 2853, 1675, 1611, 1512, 1447, 1263,
1248, 1205, 1178, 1119, 1035, 981, 923 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for
C21H28NO3 342.2064; Found 342.2064; [α]25 –316.96 (c 12.93, CHCl3, 95% ee).
(S)-6-allyl-2-morpholino-6-(4-(trifluoromethyl)benzyl)cyclohex-2-en-1-one (2j)
Prepared according to general procedure A using substrate 1j. The product was purified by flash
column chromatography (SiO2, 5–20% acetone in hexanes) to yield enaminone 2j (154 mg, 0.406
mmol, 87% yield) as a pale yellow oil; Rf = 0.20 (40% Et2O in hexanes); 1H NMR (500 MHz,
CDCl3) δ 7.49 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.8 Hz, 2H), 5.88 (t, J = 4.5 Hz, 1H), 5.77 (dddd, J
= 17.0, 10.1, 7.8, 6.8 Hz, 1H), 5.13 (ddt, J = 10.1, 2.0, 1.0 Hz, 1H), 5.08 (dq, J = 16.9, 1.5 Hz, 1H),
3.84 – 3.77 (m, 4H), 3.20 (d, J = 13.5 Hz, 1H), 2.83 – 2.76 (m, 2H), 2.75 – 2.68 (m, 3H), 2.51 –
2.35 (m, 3H), 2.22 (dd, J = 14.0, 7.8 Hz, 1H), 1.79 (dt, J = 13.8, 5.3 Hz, 1H), 1.70 (ddd, J = 14.0,
8.4, 5.6 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 198.6, 146.2, 142.1, 133.5, 131.2, 128.7 (q, J =
32.3 Hz), 127.7, 125.5, 125.3, 124.9 (q, J = 3.8 Hz), 123.3, 119.1, 66.9, 50.6, 50.0, 40.4, 39.8,
29.9, 21.8; 19F NMR (470 MHz, CDCl3) δ 62.4; IR (Neat Film, NaCl): 2928, 2855, 2817, 1678,
1616, 1448, 1325, 1263, 1163, 1119, 1067, 1019, 982, 923 cm-1; HRMS (ESI-APCI) m/z: [M+H]+
calc’d for C21H25NO2F 380.1832; Found 380.1835; [α]25 –22.43 (c 8.54, CHCl3, 92% ee).
(S)-6-methyl-6-(2-methylallyl)-2-morpholinocyclohex-2-en-1-one (2k)
Prepared according to general procedure A using substrate 1k. The product was purified by flash
column chromatography (20% EtOAc in hexanes) to afford enaminone 2k as a colorless oil (25
mg, 100 µmol 92% yield); 1H NMR (500 MHz, CDCl3) δ 5.89 (t, J = 4.5 Hz, 1H), 4.82 (dt, J =
2.9, 1.5 Hz, 1H), 4.65 (dq, J = 1.9, 0.9 Hz, 1H), 3.84 – 3.76 (m, 4H), 2.91 (ddd, J = 11.5, 6.1, 3.4
Hz, 2H), 2.64 (ddd, J = 10.2, 4.7, 2.1 Hz, 2H), 2.51 (dd, J = 13.5, 1.1 Hz, 1H), 2.45 – 2.40 (m,
ON
OCF3
OMe
NO
Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
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2H), 2.18 (dd, J = 13.6, 0.8 Hz, 1H), 1.90 (ddd, J = 13.7, 7.0, 5.8 Hz, 1H), 1.72 – 1.67 (m, 1H),
1.66 (s, 3H), 1.10 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 199.1, 145.6, 138.9, 125.1, 116.7, 67.0,
50.5, 46.1, 45.6, 32.8, 22.5, 21.8; IR (Neat Film, NaCl) 2931, 2855, 1679, 1263, 1120cm-1; HRMS
(ESI) m/z: [M+H]+ calc’d for C14H21NClO2 270.1261; Found 270.1259; [α]25 –7.5 (c 0.8, CHCl3,
99% ee).
(S)-6-(2-chloroallyl)-6-methyl-2-morpholinocyclohex-2-en-1-one (2l)
Prepared according to general procedure A using substrate 1l. The product was purified by flash
column chromatography (20% EtOAc in hexanes) to afford enaminone 2l as a colorless oil (25
mg, 93 µmol, 58% yield); 1H NMR (500 MHz, CDCl3) δ 5.91 (t, J = 4.5 Hz, 1H), 5.28 (d, J = 0.7
Hz, 1H), 5.15 (s, 1H), 3.84 – 3.78 (m, 4H), 2.93 – 2.88 (m, 2H), 2.85 (dd, J = 14.3, 0.9 Hz, 1H),
2.71 – 2.65 (m, 2H), 2.53 (d, J = 14.3 Hz, 1H), 2.46 (dtd, J = 5.3, 4.3, 2.6 Hz, 2H), 2.03 (ddd, J =
13.6, 7.4, 6.2 Hz, 1H), 1.84 – 1.79 (m, 1H), 1.17 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 199.1,
145.6, 138.9, 125.1, 116.7, 67.0, 50.5, 46.1, 45.6, 32.8, 22.5, 21.8; IR (Neat Film, NaCl) 2931,
2855, 1679, 1263, 1120cm-1; HRMS (ESI) m/z: [M+H]+ calc’d for C14H21NClO2 270.1261; Found
270.1259; [α]25 –7.5 (c 0.8, CHCl3, 99% ee).
(S)-6-allyl-6-methyl-2-(piperidin-1-yl)cyclohex-2-en-1-one (2m)
Prepared according to general procedure A using substrate 1m. The product was purified by flash
column chromatography (SiO2, 10–20% acetone in hexanes) to yield enaminone 2m (107 mg,
0.459 mmol, 99% yield) as a colorless oil; Rf = 0.37 (40% Et2O in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.84 (t, J = 4.5 Hz, 1H), 5.73 (ddt, J = 15.0, 10.2, 7.5 Hz, 1H), 5.04 – 5.01 (m, 2H), 2.70
(dt, J = 10.8, 5.2 Hz, 2H), 2.60 (dt, J = 11.2, 5.2 Hz, 2H), 2.45 – 2.30 (m, 3H), 2.21 (dd, J = 13.8,
7.6 Hz, 1H), 1.84 (dt, J = 12.7, 6.0 Hz, 1H), 1.72 – 1.61 (m, 5H), 1.55 – 1.41 (m, 2H), 1.07 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 200.8, 147.0, 134.4, 124.6, 118.0, 51.6, 45.5, 41.4, 33.4, 26.1, 24.5,
OMe
NO
Cl
OMe
N
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S11
22.1, 22.0; IR (Neat Film, NaCl): 2931, 2852, 2798, 1680, 1613, 1451, 1384, 1217, 1093, 996,
913 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C15H24NO 234.1852; Found 234.1847; [α]25
–172.28 (c 6.64, CHCl3, 99% ee).
(S)-6-allyl-3,6-dimethyl-2-morpholinocyclohex-2-en-1-one (2n)
Prepared according to general procedure A using substrate 1n. The product was purified by flash
column chromatography (SiO2, 10–20% Et2O in hexanes) to yield enaminone 2n (60.2 mg, 0.241
mmol, 52% yield) as a pale yellow oil; Rf = 0.35 (29% Et2O in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.72 (ddt, J = 16.8, 10.2, 7.4 Hz, 1H), 5.06 – 5.01 (m, 2H), 3.71 – 3.66 (m, 4H), 2.95 –
2.87 (m, 4H), 2.42 – 2.30 (m, 2H), 2.29 – 2.24 (m, 1H), 2.20 – 2.16 (m, 1H), 1.99 (s, 2H), 1.82
(ddd, J = 13.7, 6.4, 5.6 Hz, 1H), 1.67 (ddd, J = 13.6, 7.2, 5.6 Hz, 1H), 1.03 (s, 3H).; 13C NMR (125
MHz, CDCl3) δ 202.0, 153.4, 141.6, 134.3, 118.0, 77.4, 77.2, 76.9, 68.1, 50.6, 44.9, 41.3, 32.5,
28.7, 21.8, 19.8; IR (Neat Film, NaCl): 2912, 2847, 1664, 1452, 1374, 1294, 1259, 1190, 1114,
988, 911 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C15H24NO2 250.1802; Found 250.1803;
[α]25 30.71 (c 3.52, CHCl3, 90% ee).
(S)-3-allyl-3-methyl-[1,1'-bi(cyclohexan)]-6-en-2-one (2o)
Prepared according to general procedure A using substrate 1o. The product was purified by flash
column chromatography (SiO2, 5% Et2O in hexanes) to yield enaminone 2o (11 mg, 47 µmol, 93%
yield) as a pale yellow oil; Rf = 0.43 (5% Et2O in hexanes); 1H NMR (500 MHz, CDCl3) δ 6.50
(td, J = 4.1, 1.0 Hz, 1H), 5.73 (ddt, J = 16.8, 10.3, 7.4 Hz, 1H), 5.07 – 5.01 (m, 2H), 2.55 – 2.48
(m, 1H), 2.41 – 2.27 (m, 3H), 2.17 (ddt, J = 13.7, 7.6, 1.2 Hz, 1H), 1.94 – 1.79 (m, 1H), 1.77 –
1.60 (m, 6H), 1.34 (qt, J = 12.5, 3.2 Hz, 2H), 1.20 – 1.11 (m, 1H), 1.09 – 0.96 (m, 5H); 13C NMR
(125 MHz, CDCl3) δ 203.2, 143.4, 140.5, 134.5, 117.9, 44.4, 41.4, 36.4, 33.3, 33.1, 32.7, 26.9,
26.9, 26.6, 23.0, 22.0; IR (Neat Film, NaCl): 2922, 2849, 1669, 1448, 1175, 911 cm-1; HRMS
OMe
NO
Me
OMe
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S12
(ESI-APCI) m/z: [M+H]+ calc’d for C16H25O 233.1900; Found 233.1892; [α]25 –1.176 (c 0.43,
CHCl3, 72% ee).
(R)-5-allyl-5-methyl-2-morpholinocyclopent-2-en-1-one (2p)
Prepared according to general procedure A using substrate 1p. The product was purified by flash
column chromatography (SiO2, 10% acetone in hexanes) to yield enaminone 2p (97 mg, 0.438
mmol, 94% yield) as a pale tan oil; Rf = 0.23 (20% acetone in hexanes); 1H NMR (500 MHz,
CDCl3) δ 6.54 – 6.48 (m, 1H), 5.85 (ddt, J = 17.2, 10.5, 5.6 Hz, 1H), 5.27 (dq, J = 17.2, 1.6 Hz,
1H), 5.20 (dq, J = 10.5, 1.3 Hz, 1H), 4.64 – 4.52 (m, 2H), 2.59 – 2.50 (m, 1H), 2.50 – 2.40 (m,
2H), 2.38 – 2.26 (m, 1H), 1.92 – 1.81 (m, 1H), 1.80 – 1.60 (m, 5H), 1.55 (s, 1H), 1.40 – 1.22 (m,
5H), 1.21 – 1.04 (m, 2H), 1.04 – 0.92 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 209.1, 149.3, 133.9,
131.6, 118.2, 66.7, 48.6, 46.8, 42.7, 37.2, 24.0; IR (Neat Film, NaCl): 2960, 2913, 2853, 1703,
1611, 1451, 1380, 1261, 1120, 1020, 993 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for
C13H20NO2 222.1489; Found 222.1490; [α]25 –263.53 (c 6.76, CHCl3, 83% ee).
Large Scale Palladium-Catalyzed Allylic Alkylation Reactions
An oven-dried round bottom flask charged with a stir bar was cycled into a glove box under an
atmosphere of N2. To the flask were then added Pd2(dmdba)3 (78.5 mg, 61.5 µmol, 0.5 mol %)
and (S)-t-BuPHOX ligand (62.0 mg, 0.160 mmol, 1.3 mol %). The flask was then sealed with a
rubber septum and removed from the glovebox. A nitrogen line was then affixed and remained
throughout the course of the reaction. EtOAc (32 mL) was then added to the flask and the catalyst
mixture was let stir at 40 ºC in a pre-heated oil bath (ca. 30 minutes). At this point, a solution of
allyl b-ketoester (1, 3.44 g, 12.3 mmol, 1.00 equiv) in EtOAc (5.3 mL, final concentration of 0.33
M with respect to 1) was added. The reaction mixture was stirred at 40 °C in a pre-heated oil bath
O
NO Me
O
OMe
O Pd2(dmdba)3 (0.5 mol%)
EtOAc, 40 ºC, 9 h
OMe
N NOO
(S)-2a(±)-1a
(S)-t-BuPHOX (1.3 mol%)
93% yield, 98% ee[12.3 mmol scale]
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S13
until the reaction was complete as indicated by TLC analysis (20% acetone/hexanes). The reaction
mixture was concentrated in vacuo and the crude material was purified by flash column
chromatography (SiO2, 5–10% acetone in hexanes) to yield enaminone 2a as a colorless oil (2.69
g, 11.4 mmol, 93% yield, 98% ee). Rf = 0.22 (20% acetone in hexanes). Characterization data
provided above.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S14
Determination of Enantiomeric Excess
compound assay methodand conditions
retention timeof major isomer
(min)
retention timeof minor isomer
(min)%eeentry
1 SFC, 5% iPrOH in CO22.5 mL/min, AD-H col.
5.91 5.62 99
OMe
NO
2a
2 HPLC, 5% iPrOH in hexanes1 mL/min, OD-H col.
8.77 9.14 98
OEt
NO
2b
3 SFC, 3% iPrOH in CO22.5 mL/min, AD-H col.
4.45 3.95 99
ON
O
2c
4 SFC, 2% iPrOH in CO22.5 mL/min, OD-H col.
3.59 4.10 99
ON
O
2d
5 SFC, 10% MeOH in CO25 mL/min, AD-H col.
3.43 1.75 97
ON
O
2e
6 SFC, 10% iPrOH in CO25 mL/min, AD-H col.
2.27 1.81 94
ON
O
2f
CO2Me
OTBS
OTBS
MeO
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S15
compound assay methodand conditions
retention timeof major isomer
(min)
retention timeof minor isomer
(min)%eeentry
7 SFC, 10% iPrOH in CO25 mL/min, AD-H col.
2.19 2.40 94
ON
O
2g
8 SFC, 8% MeOH in CO25 mL/min, OJ-H col.
2.41 2.63 96
OBn
NO
2h
9 SFC, 5% MeOH in CO25 mL/min, OD-H col.
6.29 6.99 95
2i
CN
ON
OOMe
10 SFC, 5% iPrOH in CO25 mL/min, OJ-H col.
3.88 4.52 92
2j
ON
OCF3
13 HPLC, 3% EtOH in hexanes1 mL/min, AD col.
9.01 9.84 99
OMe
N
2m
12 SFC, 5% iPrOH in hexanes2.5 mL/min, OD-H col.
10.2 9.4 99
OMe
NO
2l
11 SFC, 5% iPrOH in hexanes2.5 mL/min, AD-H col.
8.6 7.8 99
OMe
NO
2k
Me
Cl
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S16
compound assay methodand conditions
retention timeof major isomer
(min)
retention timeof minor isomer
(min)%eeentry
14 HPLC, 1.5% iPrOH in hexanes1 mL/min, OD-H col.
8.99 8.40 90
ON
O
2n
15
HPLC, 3% iPrOH in hexanes1 mL/min, OD-H col.
14.22 17.7 83
2p
O
NO
16
SFC, 10% iPrOH in CO22.5 mL/min, AD col.
3.08 3.52 72
O
2o
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S17
Synthesis of Allylic Alkylation Substrates
Allyl 1-methyl-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1a)
General procedure B: To a solution of diisopropylamine (1.77 mL, 12.7 mmol, 1.29 equiv) in
THF (50 mL) at 0 ºC was dropwise added a solution of n-butyllithium in hexanes (5.51 mL, 2.19
M, 12.1 mmol, 1.22 equiv). The solution was stirred for 30 minutes at 0 ºC, then cooled to –78 °C.
To the reaction was then dropwise added a solution of 2-morpholinocyclohex-2-en-1-one3 (1.79
g, 9.88 mmol, 1.00 equiv) in THF (8.0 mL, 1.2 M) at –78 ºC. The mixture was stirred for 90
minutes, quenched with saturated aqueous NH4Cl (50 mL) and water (50 mL), diluted with EtOAc
(100 mL) and the phases were separated. The aqueous portion was again extracted with EtOAc
(100 mL). The combined organic fractions were dried over Na2SO4, filtered, and concentrated in
vacuo to yield the crude b-ketoester as a pale-yellow oil [confirmed to be the desired acylated
compound by crude 1H NMR analysis]. A portion (531 mg, 2.00 mmol, 1.00 equiv) of this crude
intermediate was taken up in acetone (10 mL, 0.20 M). Potassium carbonate (553 mg, 4.00 mmol,
2.0 equiv) and MeI (149 µL, 2.40 mmol, 1.20 equiv) were then added. The reaction mixture was
heated to 50 °C for 10 hours. Upon completion, the reaction mixture was cooled to room
temperature, filtered using a fritted funnel, and rinsed with 10 mL Et2O. The filtrate was
concentrated in vacuo and purified by flash column chromatography (SiO2, 4–8% acetone in
hexanes) to yield enaminone 1a (347 mg, 1.24 mmol, 62% yield over 2 steps) as a pale yellow oil;
Rf = 0.45 (50% EtOAc in hexanes); 1H NMR (500 MHz, CDCl3) δ 5.87 – 5.73 (m, 2H), 5.27 (dq,
J = 17.2, 1.5 Hz, 1H), 5.21 (dq, J = 10.4, 1.2 Hz, 1H), 4.61 – 4.53 (m, 2H), 3.81 (ddd, J = 11.3,
6.3, 3.1 Hz, 2H), 3.76 (ddd, J = 11.3, 6.4, 2.9 Hz, 2H), 2.99 – 2.96 (m, 2H), 2.63 – 2.55 (m, 2H),
2.54 – 2.49 (m, 1H), 2.47 – 2.42 (m, 1H), 2.36 (dtd, J = 19.1, 5.4, 3.1 Hz, 1H), 1.84 (ddd, J = 13.6,
9.7, 5.6 Hz, 1H), 1.37 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 193.9, 172.4, 146.4, 131.6, 124.0
118.9, 66.9, 66.0, 54.2, 50.0, 33.3, 22.7, 20.6; IR (Neat Film, NaCl): 3447 (broad), 2955, 2855,
2067, 1733, 1695, 1617, 1450, 1378, 1264, 1248, 1222, 1175, 1145, 1119, 1020, 992, 948 cm-1;
HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C15H22NO4 280.1543; Found 280.1554.
ON
O ON
O
1a
MeO
O1) LDA, THF, –78 ºC;then, allyl chloroformate
2) MeI, K2CO3,acetone, 50 ºC
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S18
Allyl 1-ethyl-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1b)
Prepared according to general procedure B using ethyl iodide. The product was purified by flash
column chromatography (SiO2, 4–20% EtOAc in hexanes) to yield enaminone 1b (468 mg, 1.60
mmol, 74% yield over 2 steps) as a pale-yellow oil. Rf = 0.53 (50% EtOAc in hexanes); 1H NMR
(400 MHz, CDCl3) δ 5.83 (ddt, J = 17.2, 10.4, 5.8 Hz, 1H), 5.73 (ddd, J = 4.5, 3.5, 1.2 Hz, 1H),
5.27 (dq, J = 17.2, 1.5 Hz, 1H), 5.21 (dq, J = 10.4, 1.2 Hz, 1H), 4.57 (dq, J = 5.8, 1.5 Hz, 2H), 3.80
(ddd, J = 11.4, 6.4, 3.1 Hz, 1H), 3.75 (ddd, J = 11.3, 6.3, 3.0 Hz, 1H), 2.97 – 2.93 (m, 2H), 2.60 –
2.52 (m, 3H), 2.44 – 2.33 (m, 2H), 1.95 (dq, J = 13.9, 7.5 Hz, 1H), 1.86 (ddd, J = 13.0, 9.6, 5.4
Hz, 1H), 1.78 (dq, J = 13.9, 7.5 Hz, 1H), 0.92 (t, J = 7.5 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
193.6, 171.3, 146.8, 131.7, 128.2, 123.5, 119.0, 67.0, 65.8, 57.9, 50.0, 29.8, 27.0, 22.6, 9.1; IR
(Neat Film, NaCl): 2961, 2855, 1732, 1694, 1617, 1448, 1378, 1300, 1264, 1220, 1167, 1120, 957,
934 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C16H24NO4 294.1700; Found 294.1690.
Allyl 1-(2-((tert-butyldimethylsilyl)oxy)ethyl)-3-morpholino-2-oxocyclohex-3-ene-1-
carboxylate (1d)
Synthesized according to general procedure B using (2-bromoethoxy)(tert-butyl)dimethylsilane
and cesium carbonate in place of potassium carbonate. The product was purified by flash column
chromatography (SiO2, 5–20% EtOAc in hexanes) to yield enaminone 1d (184 mg, 0.434 mmol,
49% yield over 2 steps) as a pale tan oil; Rf = 0.23 (20% EtOAc in hexanes); 1H NMR (500 MHz,
CDCl3) δ 5.83 (ddt, J = 17.2, 10.4, 5.9 Hz, 1H), 5.78 – 5.70 (m, 1H), 5.27 (dq, J = 17.2, 1.5 Hz,
1H), 5.21 (dq, J = 10.5, 1.2 Hz, 1H), 4.60 – 4.52 (m, 2H), 3.82 – 3.66 (m, 6H), 2.96 – 2.29 (m,
2H), 2.59 – 2.46 (m, 4H), 2.38 (dtd, J = 19.0, 5.5, 2.9 Hz, 1H), 2.14 (ddd, J = 13.8, 7.6, 6.1 Hz,
1H), 1.98 – 1.89 (m, 2H), 0.86 (s, 9H), 0.02 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 193.3, 171.0,
146.5, 131.7, 123.7, 119.1, 66.9, 66.0, 59.7, 56.5, 50.0, 36.8, 30.8, 26.0, 22.7, 18.4, -5.2; IR (Neat
ON
OEt
O
O
ON
OO
O
OTBS
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S19
Film, NaCl): 2955, 2928, 2855, 1733, 1695, 1616, 1447, 1378, 1263, 1209, 1120, 1100, 981, 935
cm-1; HRMS (ESI) m/z: [M+H]+ calc’d for C22H38NO5Si 424.2514; Found 424.2521.
Allyl 1-(3-methoxy-3-oxopropyl)-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1e)
Prepared according to general procedure B using methyl acrylate. The product was purified by
flash column chromatography (SiO2, 10–20% acetone in hexanes) to yield enaminone 1e (223 mg,
0.635 mmol, 58% yield over 2 steps) as a yellow oil; Rf = 0.42 (50% EtOAc in hexanes); 1H NMR
(500 MHz, CDCl3) δ 5.80 (ddt, J = 17.3, 10.4, 5.9 Hz, 1H), 5.73 – 5.67 (m, 1H), 5.25 (dd, J = 17.2,
1.5 Hz, 1H), 5.19 (dd, J = 10.4, 1.3 Hz, 1H), 4.60 – 4.48 (m, 2H), 3.76 (ddd, J = 11.3, 6.4, 3.1 Hz,
2H), 3.71 (ddd, J = 11.4, 6.4, 3.0 Hz, 2H), 2.92 (ddd, J = 11.7, 6.3, 3.0 Hz, 2H), 2.56 – 2.41 (m,
4H), 2.40 – 2.27 (m, 3H), 2.18 (ddd, J = 14.0, 10.6, 5.6 Hz, 1H), 2.04 (ddd, J = 14.1, 10.8, 5.4 Hz,
1H), 1.84 (ddd, J = 14.5, 9.8, 6.1 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 193.1, 173.4, 170.9,
146.6, 131.4, 123.3, 119.2, 66.8, 66.1, 56.7, 51.7, 49.8, 30.7, 29.5, 28.9, 22.5; IR (Neat Film,
NaCl): 2953, 2854, 2820, 1733, 1694, 1616, 1447, 1377, 1264, 1209, 1177, 1120, 983, 957 cm-1;
HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C18H26NO6 352.1755; Found 352.1771.
Allyl 3-morpholino-2-oxo-1-(3-oxobutyl)cyclohex-3-ene-1-carboxylate (1f)
Prepared according to general procedure B using methyl vinyl ketone. The product was purified
by flash column chromatography (SiO2, 20–65% EtOAc in hexanes) to yield enaminone 1f (537
mg, 1.60 mmol, 74% yield over 2 steps) as a pale yellow oil that solidified on storage at –20 °C;
Rf = 0.28 (50% EtOAc in hexanes); 1H NMR (500 MHz, CDCl3) δ 5.81 (ddt, J = 17.2, 10.4, 5.9
Hz, 1H), 5.75 – 5.69 (m, 1H), 5.26 (dq, J = 17.2, 1.5 Hz, 1H), 5.20 (dq, J = 10.4, 1.2 Hz, 1H), 4.59
– 4.49 (m, 2H), 3.77 (ddd, J = 11.4, 6.4, 3.1 Hz, 2H), 3.72 (ddd, J = 11.3, 6.4, 3.0 Hz, 2H), 2.93
(ddd, J = 11.9, 6.3, 3.1 Hz, 2H), 2.60 (ddd, J = 17.7, 10.3, 5.5 Hz, 1H), 2.57 – 2.49 (m, 2H), 2.52
ON
OO
O
CO2Me
ON
OO
O
MeO
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S20
– 2.39 (m, 2H), 2.41 – 2.35 (m, 1H), 2.36 – 2.32 (m, 1H), 2.10 (s, 4H), 1.98 (ddd, J = 14.1, 10.3,
5.3 Hz, 1H), 1.84 (ddd, J = 9.7, 8.1, 4.9 Hz, 1H);13C NMR (125 MHz, CDCl3) δ 207.7, 193.4,
171.2, 146.7, 131.4, 123.5, 119.3, 66.9, 66.0, 56.7, 49.9, 38.9, 31.1, 30.0, 30.0, 27.7, 22.6; IR (Neat
Film, NaCl): 2956, 2854, 1721, 1615, 1447, 1372, 1299, 1264, 1209, 1179, 1120, 1095, 982, 939
cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C18H26NO5 336.1805; Found 336.1803.
Allyl 1-(2-cyanoethyl)-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1g)
Prepared according to general procedure B using acrylonitrile. The product was purified by flash
column chromatography (SiO2, 10–20% acetone in hexanes) to yield enaminone 1g (247 mg, 0.776
mmol, 71% yield over 2 steps) as a colorless oil; Rf = 0.29 (50% EtOAc in hexanes); 1H NMR
(500 MHz, CDCl3) δ 5.83 (ddt, J = 16.5, 10.4, 6.0 Hz, 1H), 5.76 (t, J = 4.3 Hz, 1H), 5.29 (dq, J =
17.1, 1.4 Hz, 1H), 5.25 (dq, J = 10.4, 1.2 Hz, 1H), 4.64 – 4.56 (m, 2H), 3.79 (ddd, J = 11.4, 6.4,
3.1 Hz, 2H), 3.73 (ddd, J = 11.4, 6.4, 3.0 Hz, 2H), 2.95 (ddd, J = 11.8, 6.4, 3.1 Hz, 2H), 2.60 –
2.49 (m, 4H), 2.45 – 2.38 (m, 3H), 2.21 (ddd, J = 14.0, 9.5, 5.9 Hz, 1H), 2.07 (ddd, J = 14.0, 9.5,
6.3 Hz, 1H), 1.92 – 1.86 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 192.7, 170.2, 146.6, 131.1, 123.7,
119.9, 119.4, 66.8, 66.5, 56.5, 49.8, 31.1, 30.2, 22.5, 13.3; IR (Neat Film, NaCl): 2956, 2854, 2247,
1734, 1690, 1617, 1448, 1375, 1264, 1208, 1119, 982, 947 cm-1; HRMS (ESI-APCI) m/z: [M+H]+
calc’d for C17H23N2O4 319.1652, Found 319.1668.
Allyl 1-benzyl-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1h)
Prepared according to general procedure B using benzyl bromide. The product was purified by
flash column chromatography (SiO2, 4–10% acetone in hexanes) to yield enaminone 1h (498 mg,
1.40 mmol, 65% yield over 2 steps) as a colorless oil; Rf = 0.23 (20% acetone in hexanes); 1H
NMR (500 MHz, CDCl3) δ 7.26 – 7.19 (m, 3H), 7.19 – 7.14 (m, 2H), 5.79 (ddt, J = 17.3, 10.4, 5.9
Hz, 1H), 5.71 (ddd, J = 4.5, 3.3, 1.3 Hz, 1H), 5.26 (dq, J = 17.2, 1.5 Hz, 1H), 5.21 (dq, J = 10.4,
ON
OO
O
CN
ON
OBn
O
O
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S21
1.2 Hz, 1H), 3.82 (ddd, J = 11.4, 6.4, 3.0 Hz, 2H), 3.77 (ddd, J = 11.3, 6.4, 2.9 Hz, 2H), 3.26 (d, J
= 13.7 Hz, 1H), 3.14 (d, J = 13.7 Hz, 1H), 2.96 (ddd, J = 11.7, 6.4, 3.0 Hz, 2H), 2.58 – 2.51 (m,
3H), 2.40 – 2.27 (m, 2H), 1.80 – 1.74 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 192.6, 170.5, 146.8,
136.4, 131.5, 130.7, 128.2, 128.2, 126.9, 123.9, 119.2, 66.9, 66.1, 58.7, 49.9, 39.8, 30.0, 22.7; IR
(Neat Film, NaCl): 2956, 2854, 1734, 1691, 1615, 1447, 1377, 1263, 1207, 1176, 1118, 1085, 980,
937 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C21H26NO4 356.1856; Found 356.1857.
Allyl 1-(4-methoxybenzyl)-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1i)
Prepared according to general procedure B using p-methoxybenzyl chloride. The product was
purified by flash column chromatography (SiO2, 5–10% acetone in hexanes) to yield enaminone
1i (86 mg, 0.22 mmol, 21% yield over 2 steps) as a pale yellow oil; Rf = 0.72 (20% Et2O in
CH2Cl2); 1H NMR (500 MHz, CDCl3) δ 7.09 (d, J = 8.6 Hz, 2H), 6.78 (d, J = 8.7 Hz, 2H), 5.80
(ddt, J = 17.2, 10.4, 5.9 Hz, 1H), 5.72 (t, J = 4.3 Hz, 1H), 5.26 (dq, J = 17.2, 1.5 Hz, 1H), 5.22 (dq,
J = 10.4, 1.2 Hz, 1H), 4.53 (dq, J = 5.9, 1.4 Hz, 2H), 3.82 (ddd, J = 11.4, 6.4, 3.0 Hz, 2H), 3.79 –
3.75 (m, 5H), 3.19 (d, J = 13.9 Hz, 1H), 3.10 (d, J = 13.9 Hz, 1H), 2.96 (ddd, J = 11.6, 6.5, 3.1 Hz,
2H), 2.59 – 2.49 (m, 3H), 2.38 – 2.28 (m, 2H), 1.76 (ddd, J = 14.2, 10.4, 6.2 Hz, 1H); 13C NMR
(125 MHz, CDCl3) δ 192.7, 170.6, 158.6, 146.8, 131.7, 131.6, 128.3, 123.9, 119.2, 113.6, 66.9,
66.1, 58.8, 55.3, 50.0, 38.9, 30.0, 22.7; IR (Neat Film, NaCl): 2954, 2853, 1734, 1691, 1612, 1512,
1445, 1262, 1248, 1208, 1178, 1119, 1034, 981, 938 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d
for C22H28NO5 386.1962; found 386.1948.
ON
OO
O
OMe
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S22
Allyl 3-morpholino-2-oxo-1-(4-(trifluoromethyl)benzyl)cyclohex-3-ene-1-carboxylate (1j)
Prepared according to general procedure B using p-trifluoromethylbenzyl bromide. The product
was purified by flash column chromatography (SiO2, 2:1:1–2:2:1 hexanes:DCM:acetone) to yield
enaminone 1j (276 mg, 0.652 mmol, 60% yield over 2 steps) as a pale yellow oil; Rf = 0.78 (20%
Et2O in CH2Cl2); 1H NMR (500 MHz, CDCl3) δ 7.50 (d, J = 7.8 Hz, 2H), 7.32 (d, J = 7.5 Hz, 2H),
5.80 – 5.69 (m, 2H), 5.28 – 5.18 (m, 2H), 4.51 (dq, J = 5.9, 1.5 Hz, 2H), 3.83 (ddd, J = 11.4, 6.4,
3.0 Hz, 2H), 3.77 (ddd, J = 11.4, 6.4, 2.9 Hz, 2H), 3.29 (d, J = 13.6 Hz, 1H), 3.19 (d, J = 13.6 Hz,
1H), 2.97 (ddd, J = 11.8, 6.4, 3.0 Hz, 2H), 2.59 – 2.50 (m, 3H), 2.38 – 2.32 (m, 2H), 1.78 (ddd, J
= 14.2, 10.4, 6.2 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 192.3, 170.3, 146.8, 140.7, 131.3, 131.2,
129.2 (q, J = 32.4 Hz), 125.3, 125.1 (q, J = 3.8 Hz), 123.8, 123.3, 119.5, 66.9, 66.3, 58.7, 49.9,
39.6, 30.4, 22.7; 19F NMR (470 MHz, CDCl3) δ 62.5; IR (Neat Film, NaCl): 2957, 2855, 1732,
1694, 1618, 1447, 1418, 1323, 1263, 1209, 1162, 1116, 1066, 1019, 981, 938 cm-1; HRMS (ESI-
APCI) m/z: [M+H]+ calc’d for C22H25NO4F 424.1730; Found 424.1737.
2-Methylallyl 1-methyl-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1k)
Prepared according to general procedure B using 2-methylallyl cyanoformate (SI3, vida infra).
The product was purified by flash column chromatography (20–24% EtOAc/hexanes) to yield
enaminone 1k as a slightly yellow oil (808 mg, 2.76 mmol, 56% yield over 2 steps). 1H NMR (500
MHz, CDCl3) δ 5.79 (ddd, J = 4.9, 3.5, 1.1 Hz, 1H), 4.92 (d, J = 10.9 Hz, 2H), 4.50 (d, J = 12.7
Hz, 1H), 3.82 (ddd, J = 11.4, 6.4, 3.0 Hz, 2H), 3.77 (ddd, J = 11.3, 6.4, 2.9 Hz, 2H), 3.00 (ddd, J
= 11.1, 4.9, 2.0 Hz, 2H), 2.61 – 2.51 (m, 3H), 2.47 (dddd, J = 13.5, 5.1, 3.1, 1.2 Hz, 1H), 2.39 (dtd,
J = 19.0, 5.4, 3.1 Hz, 1H), 1.87 (ddd, J = 13.5, 9.7, 5.6 Hz, 1H), 1.71 (s, 3H), 1.41 (s, 3H); 13C
NMR (125 MHz, CDCl3) δ 193.7, 172.3, 146.3, 139.4, 123.9, 113.5, 68.4, 66.8, 54.1, 49.8, 33.3,
ON
OO
O
CF3
ON
OMe
O
O
Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S23
22.6, 20.6, 19.5; IR (Neat Film, NaCl) 2936, 2854, 1737, 1694, 1615, 1450, 1175, 1119, cm-1;
HRMS (ESI) m/z: [M+H]+ calc’d for C16H24NO4 294.1700; found 294.1705.
2-Chloroallyl 1-methyl-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1l)
Prepared according to general procedure B using 2-chloroallyl cyanoformate (SI1, vida infra). The
product was purified by flash column chromatography (20–22% EtOAc/hexanes) to yield
enaminone 1l as a slightly yellow oil (470 mg, 1.50 mmol, 37% yield over 2 steps); 1H NMR (500
MHz, CDCl3) δ 5.82 (ddd, J = 5.0, 3.6, 1.0 Hz, 1H), 5.44 (dt, J = 1.8, 1.2 Hz, 1H), 5.40 (d, J = 1.7
Hz, 1H), 4.72 (ddd, J = 13.5, 1.2, 0.6 Hz, 1H), 4.63 (ddd, J = 13.5, 1.2, 0.6 Hz, 1H), 3.83 (ddd, J
= 11.4, 6.4, 3.1 Hz, 2H), 3.78 (ddd, J = 11.3, 6.3, 3.0 Hz, 2H), 3.00 (ddd, J = 9.6, 6.2, 3.1 Hz, 2H),
2.65 – 2.50 (m, 3H), 2.51 – 2.46 (m, 1H), 2.41 (dtd, J = 19.0, 5.4, 3.3 Hz, 1H), 1.89 (ddd, J = 13.5,
9.4, 5.5 Hz, 1H), 1.43 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 193.5, 171.9, 146.3, 135.4, 124.3,
115.8, 66.9, 66.7, 54.2, 49.9, 33.3, 22.6, 20.6; IR (Neat Film, NaCl) 2954, 2855, 1741, 1693, 1450,
1377 cm-1; HRMS (ESI) m/z: [M+H]+ calc’d for C15H21NClO4 314.1154; Found 314.1156.
Allyl 1-methyl-2-oxo-3-(piperidin-1-yl)cyclohex-3-ene-1-carboxylate (1m)
Prepared according to general procedure B using 2-(piperidin-1-yl)cyclohex-2-en-1-one.3 The
product was purified by flash column chromatography (SiO2, 8–16% Et2O in hexanes) to yield
enaminone 1m (427 mg, 1.54 mmol, 59% yield over 2 steps) as a pale tan oil; Rf = 0.32 (40% Et2O
in hexanes; 1H NMR (500 MHz, CDCl3) δ 5.77 (ddt, J = 17.2, 10.4, 5.7 Hz, 1H), 5.69 (ddd, J =
4.8, 3.5, 1.0 Hz, 1H), 5.21 (dd, J = 17.2, 1.5 Hz, 1H), 5.14 (dd, J = 10.5, 1.3 Hz, 1H), 4.55 – 4.47
(m, 2H), 2.81 (ddd, J = 11.2, 7.2, 3.6 Hz, 2H), 2.46 (dddt, J = 18.1, 9.2, 5.4, 3.3 Hz, 3H), 2.37
(dddd, J = 13.6, 5.1, 3.2, 1.1 Hz, 1H), 2.29 (dtd, J = 19.0, 5.4, 3.2 Hz, 1H), 1.77 (ddd, J = 13.4,
9.6, 5.6 Hz, 1H), 1.65 – 1.53 (m, 4H), 1.46 – 1.41 (m, 2H), 1.31 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 194.0, 172.3, 147.7, 131.8, 123.5, 118.7, 65.8, 54.2, 51.0, 33.4, 26.0, 24.5, 22.8, 20.7;
ON
OMe
O
O
Cl
ON
MeO
O
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S24
IR (Neat Film, NaCl): 2934, 2851, 2802, 1735, 1696, 1613, 1452, 1387, 1248, 1222, 1175, 1110,
987, 943 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C16H24NO3 278.1751; Found 278.1747.
Allyl 1,4-dimethyl-3-morpholino-2-oxocyclohex-3-ene-1-carboxylate (1n)
Prepared according to general procedure B using 3-methyl-2-morpholinocyclohex-2-en-1-one.4
The product was purified by flash column chromatography (SiO2, 5–20% EtOAc in hexanes) to
yield enaminone 1n (772 mg, 2.63 mmol, 74% yield over 2 steps) as a pale yellow oil; Rf = 0.34
(20% EtOAc in hexanes); 1H NMR (500 MHz, CDCl3) δ 5.82 (ddt, J = 17.2, 10.5, 5.6 Hz, 1H),
5.24 (dq, J = 17.2, 1.6 Hz, 1H), 5.18 (dq, J = 10.4, 1.3 Hz, 1H), 4.58 (ddt, J = 13.3, 5.5, 1.5 Hz,
1H), 4.53 (ddt, J = 13.3, 5.6, 1.4 Hz, 1H), 3.70 – 3.63 (m, 4H), 2.99 – 2.90 (m, 2H), 2.90 – 2.81
(m, 2H), 2.49 (dddd, J = 19.2, 9.8, 5.3, 1.1 Hz, 1H), 2.38 (ddd, J = 13.6, 5.2, 3.6 Hz, 1H), 2.28
(dddd, J = 19.1, 5.6, 3.6, 0.9 Hz, 1H), 1.95 (s, 3H), 1.79 (ddd, J = 13.6, 9.7, 5.5 Hz, 1H), 1.33 (s,
3H); 13C NMR (125 MHz, CDCl3) δ 194.8, 172.5, 153.2, 142.1, 131.8, 118.4, 67.9, 65.7, 53.9,
50.3, 32.3, 29.2, 20.5, 19.6; IR (Neat Film, NaCl): 2935, 2848, 1734, 1680, 1452, 1375, 1259,
1190, 1168, 1114, 1070, 989 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C16H24NO4 294.1700; Found 294.1701.
Allyl 3-methyl-2-oxo-[1,1'-bi(cyclohexan)]-6-ene-3-carboxylate (1o)
Prepared according to general procedure B using [1,1'-bi(cyclohexan)]-6-en-2-one.5 The product
was purified by flash column chromatography (SiO2, 10% Et2O in DCM) to yield enone 1o (51
mg, 0.185 mmol, 30% yield over 2 steps) as a pale yellow oil; Rf = 0.33 (10% Et2O in hexanes); 1H NMR (500 MHz, CDCl3) δ 6.51 (dt, J = 4.4, 2.2 Hz, 1H), 5.84 (ddt, J = 17.2, 10.5, 5.6 Hz, 1H),
5.26 (dd, J = 17.2, 1.5 Hz, 1H), 5.20 (dd, J = 10.4, 1.4 Hz, 1H), 4.57 (tt, J = 5.5, 1.4 Hz, 2H), 2.57
– 2.42 (m, 3H), 2.35 – 2.27 (m, 1H), 1.89 – 1.80 (m, 1H), 1.77 – 1.61 (m, 6H), 1.37 (s, 3H), 1.36
– 1.29 (m, 2H), 1.19 – 1.07 (m, 2H), 1.02 – 0.93 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 196.8,
ON
OMe
O
O
Me
OMe
O
O
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S25
172.8, 144.2, 140.9, 131.9, 118.5, 65.8, 53.6, 36.8, 33.4, 32.8, 32.3, 26.9, 26.8, 26.5, 23.6, 20.6;
IR (Neat Film, NaCl): 2925, 2851, 1734, 1684, 1379, 1351, 1299, 1247, 1167, 1110, 981, 935 cm-
1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C17H25O3 277.1798; Found 277.1791.
Allyl 1-methyl-3-morpholino-2-oxocyclopent-3-ene-1-carboxylate (1p)
Prepared according to general procedure B using 2-morpholinocyclopent-2-en-1-one.6 The
product was purified by flash column chromatography (SiO2, 2–10% EtOAc in DCM) to yield
enaminone 1p (151 mg, 0.570 mmol, 21% yield over 2 steps) as a pale orange oil; Rf = 0.33 (10%
EtOAc in CH2Cl2); 1H NMR (500 MHz, CDCl3) δ 6.39 (t, J = 3.2 Hz, 1H), 5.85 (ddt, J = 17.2,
10.5, 5.5 Hz, 1H), 5.27 (dq, J = 17.2, 1.6 Hz, 1H), 5.20 (dq, J = 10.5, 1.3 Hz, 1H), 4.58 (dt, J =
5.5, 1.5 Hz, 2H), 3.79 (ddd, J = 5.2, 3.9, 0.8 Hz, 4H), 3.19 – 3.15 (m, 2H), 3.05 – 3.01 (m, 3H),
2.38 (dd, J = 18.2, 3.2 Hz, 1H), 1.42 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 201.8, 171.6, 148.6,
131.9, 131.8, 118.3, 66.6, 65.9, 54.1, 48.5, 37.8, 21.1; IR (Neat Film, NaCl): 2962, 2933, 2855,
1740, 1707, 1612, 1452, 1379, 1263, 1178, 1120, 1068, 1022, 994 cm-1; HRMS (ESI-APCI) m/z:
[M+H]+ calc’d for C14H20NO4 266.1387; Found 266.1391.
Allyl 1-(((tert-butyldimethylsilyl)oxy)methyl)-3-morpholino-2-oxocyclohex-3-ene-1-
carboxylate (1c)
To a solution of diisopropylamine (1.77 mL, 12.7 mmol, 1.29 equiv) in THF (50 mL) at 0 ºC was
dropwise added a solution of n-butyllithium in hexanes (5.51 mL, 2.19 M, 12.1 mmol, 1.22 equiv).
The solution was stirred for 30 minutes at 0 ºC, then cooled to –78 °C. To the reaction was then
dropwise added a solution of 2-morpholinocyclohex-2-en-1-one3 (1.79 g, 9.88 mmol, 1.00 equiv)
in THF (8.0 mL, 1.2 M) at –78 ºC. The mixture was stirred for 90 minutes, quenched with saturated
aqueous NH4Cl (50 mL) and water (50 mL), diluted with EtOAc (100 mL) and the phases were
separated. The aqueous portion was again extracted with EtOAc (100 mL). The combined organic
O
NMe
O
OO
ON
OO
O
OTBS
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S26
fractions were dried over Na2SO4, filtered, and concentrated in vacuo to yield the crude b-ketoester
as a pale-yellow oil [confirmed to be the desired acylated compound by crude 1H NMR analysis].
A portion (218 mg, 0.822 mmol, 1.00 equiv) of this crude intermediate was dissolved in THF (1.6
mL, 0.5 M) and cooled to 0 °C. Potassium carbonate (247 mg, 2.47 mmol, 3.0 equiv) and 37%
aqueous formaldehyde (156 µL, 5.67 mmol, 6.9 equiv) were added. The reaction was warmed to
23 °C and stirred for 4 hours. Upon completion, the reaction mixture was extracted with EtOAc (2
x 5 mL). The combined organic layers were dried over Na2SO4, filtered, concentrated in vacuo,
and purified by flash column chromatography (SiO2, 20–35% acetone in hexanes) to yield 133 mg
of a pale-yellow oil. This intermediate alcohol was taken up in CH2Cl2 (4.5 mL, 0.1 M) and TBSCl
(75 mg, 0.49 mmol, 1.1 equiv) and imidazole (61 mg, 0.90 mmol, 2.0 equiv) were added. The
reaction mixture was stirred for 8 hours, concentrated in vacuo and purified by column
chromatography (SiO2, 20–35% EtOAc in hexanes) to yield enaminone 1c (106 mg, 0.257 mmol,
29% yield over 3 steps) as a pale yellow oil; Rf = 0.25 (25% EtOAc in hexanes); 1H NMR (500
MHz, CDCl3) δ 5.88 – 5.80 (m, 2H), 5.27 (dq, J = 17.2, 1.5 Hz, 1H), 5.20 (dq, J = 10.4, 1.3 Hz,
1H), 4.60 (ddt, J = 13.2, 5.8, 1.4 Hz, 1H), 4.54 (ddt, J = 13.2, 5.7, 1.4 Hz, 1H), 4.08 (d, J = 9.8 Hz,
1H), 3.88 (d, J = 9.8 Hz, 1H), 3.83 – 3.73 (m, 4H), 2.91 – 2.85 (m, 2H), 2.68 – 2.58 (m, 3H), 2.55
– 2.49 (m, 1H), 2.44 – 2.36 (m, 1H), 2.02 (ddd, J = 13.8, 10.0, 5.8 Hz, 1H), 0.85 (s, 9H), 0.03 (s,
3H), 0.03 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 192.0, 169.6, 146.7, 131.7, 125.0, 118.8, 66.9,
66.6, 66.0, 65.4, 59.9, 50.0, 29.8, 28.0, 25.9, 25.8, 22.5, 18.3, -5.5; IR (Neat Film, NaCl): 2955,
2929, 2894, 2856, 1734, 1690, 1616, 1462, 1448, 1379, 1262, 1217, 1120, 964 cm-1; HRMS
(APCI) m/z: [M+H]+ calc’d for C21H36NO5Si 410.2357; found 410.2342.
2-chloroallyl carbonocyanidate (SI1)
Prepared according to literature precedent.7 Product vacuum distilled (62–65°C, 20 torr) to afford
the product (SI2) as a clear oil (6.13 g, 90% yield). 1H NMR (500 MHz, CDCl3) δ 5.62 – 5.59
(m, 1H), 5.57 (d, J = 2.1 Hz, 1H), 4.88 (d, J = 0.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ
143.5, 132.9, 118.5, 108.9, 69.7; IR (Neat Film, NaCl) 2249, 1759, 1640, 1230, 1180, 918 cm-1;
NC O
O
Cl
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S27
Anal. Calc’d for C5H4NO2Cl: C, 41.26%; H, 2.77%; N, 9.62%; Cl, 24.36%; Found: C, 41.22%;
H, 2.79%, N, 9.49%; Cl, 24.18%.
2-methylallyl carbonochloridate (SI2)
Prepared as reported for the 2-chloroallyl substrate from the report by Stoltz and coworkers.7 The
product was vacuum distilled (45–47 °C, 20 torr) to provide the product (SI2) as a clear oil (7.48
g, 60% yield). Spectral data matches that reported in the literature.8 1H NMR (500 MHz, CDCl3)
δ 5.10 – 5.07 (m, 1H), 5.07 – 5.04 (m, 1H), 4.71 (s, 2H), 1.81 (s, 3H); 13C NMR (125 MHz, CDCl3)
δ 150.4, 137.9, 115.8, 75.0, 19.2.
2-methylallyl carbonocyanidate (SI3)
Prepared according to procedure for cyanoformate SI1 from chloroformate SI2. Product vacuum
distilled (60°C, 35 torr) to afford the product (SI3) as a clear oil (3.61 g, 81% yield). 1H NMR (500
MHz, CDCl3) δ 5.12 – 5.06 (m, 2H), 4.73 (s, 2H), 1.81 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
144.1, 137.2, 116.4, 109.3, 72.0, 19.3; IR (Neat Film, NaCl) 2246, 1762, 1227, 1242, 918 cm-1;
Anal. Calc’d for C6H7NO2: C, 57.59%; H, 5.64%; N, 11.19%; Found: C, 57.59%; H, 5.49%; N,
11.11%.
Cl O
O
NC O
O
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S28
Derivatization of Enaminone Products
(S)-6-allyl-2-hydroxy-6-methylcyclohex-2-en-1-one (3)
Enaminone 2a (297 mg, 1.26 mmol) was diluted in MeOH/H2O (4:1). HCl (0.1 mL, 12 M aqueous)
was added by syringe. The reaction mixture was stirred at 60 °C under nitrogen for 2 h. The mixture
was cooled to room temperature and partitioned between H2O and CH2Cl2. The aqueous layer was
extracted with CH2Cl2 two additional times. The combined organic layers were dried over Na2SO4,
filtered, and concentrated. The residue was purified by flash column chromatography (1–2%
EtOAc/hexanes) to give diketone 3 (166 mg, 1.00 mmol, 79% yield) as a yellow oil. 1H NMR (300
MHz, CDCl3) δ 6.07 (s, 1H), 6.02 (t, J = 4.6 Hz, 1H), 5.68 (dddd, J = 16.4, 10.6, 7.6, 7.2 Hz, 1H),
5.09 – 4.99 (m, 2H), 2.38 – 2.30 (m, 3H), 2.18 (ddt, J = 13.8, 7.6, 1.1 Hz, 1H), 1.95 – 1.86 (m,
1H), 1.72 (ddd, J = 13.7, 6.5, 5.5 Hz, 1H), 1.10 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 200.3, 145.6,
133.5, 118.7, 117.0, 44.1, 41.1, 33.6, 21.8, 20.4; IR (Neat Film, NaCl): 3428, 3076, 2975, 2935,
1721, 1640, 1455, 1217 cm-1; HRMS (FAB+) m/z: [M+H–H2]+ calc’d for C10H13O2 165.0916;
Found 165.0916; [α]25 –5.95 (c 4.45, CHCl3).
(S)-6-allyl-6-methyl-2-(phenylamino)cyclohex-2-en-1-one (4)
Compound 2a (52 mg, 0.21 mmol, 1.0 equiv) was dissolved in toluene (1.3 mL, 0.16 M). p-
Toluenesulfonic acid monohydrate (39 mg, 0.21 mmol, 1.0 equiv) and aniline (20 µL, 0.22 mmol,
1.0 equiv) were then added to the solution of 2a. The mixture was heated to 50°C for 3.5 h. The
reaction mixture was diluted with EtOAc and washed with saturated aqueous NaHCO3 (3x). The
organic layer was then dried over Na2SO4, filtered, and concentrated in vacuo. The crude was
purified by flash column chromatography (2% EtOAc in hexanes) to yield compound 4 (18 mg,
75 µmol, 35% yield). 1H NMR (500 MHz, CDCl3) δ 7.28 – 7.24 (m, 2H), 7.05 – 7.02 (m, 2H),
6.91 (tt, J = 7.4, 1.1 Hz, 1H), 6.34 (t, J = 4.7 Hz, 1H), 5.76 (ddt, J = 16.5, 10.5, 7.4 Hz, 1H), 5.12
– 5.06 (m, 2H), 2.52 – 2.40 (m, 3H), 2.26 (ddt, J = 13.8, 7.6, 1.2 Hz, 1H), 1.98 (ddd, J = 13.6, 6.8,
OMe
HO
OPhHN
Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S29
5.4 Hz, 1H), 1.80 (ddd, J = 13.6, 6.8, 5.3 Hz, 1H), 1.17 (s, 3H) (N–H not observed in CDCl3); 13C
NMR (125 MHz, CDCl3) δ 200.0, 142.3, 134.8, 134.0, 133.9, 121.1, 118.8, 118.5, 115.0, 44.4,
41.5, 33.1, 22.2, 21.0; IR (Neat Film, NaCl): 3364, 2926, 1668, 1634, 1600, 1515, 1442, 1306,
1203, 1014, 997, 916, 750, 691 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C16H20NO 242.1539; Found 242.1535; [α]25 –4.72 (c 2.18, CHCl3).
(S)-2-allyl-2-methyl-2,3,4,9-tetrahydro-1H-carbazol-1-one (5)
To a solution of enaminone 2a (118 mg, 0.500 mmol, 1.00 equiv) toluene (2 mL, 0.25 M), p-
toluenesulfonic acid monohydrate (95 mg, 0.50 mmol, 1.0 equiv) and phenyl hydrazine (54 mg,
0.50 mmol, 1.0 equiv) were added. The reaction was heated to 60 °C and stirred for 4 hours, cooled
to room temperature, diluted with saturated aqueous NH4Cl (1 mL), and extracted with EtOAc (3x
5 mL). The combined organic fractions were dried over Na2SO4, filtered, and concentrated in
vacuo. The crude intermediate was taken up in 5 mL 4:1 AcOH:12 M HCl (0.1 M) and stirred for
2 hours at ambient temperature. Ice (ca. 10 g) was then added. The ice/reaction mixture was
quenched with 5.0 M NaOH until a pH of 9–10 was achieved. The mixture was extracted with
EtOAc (3x 20 mL). The combined organic fractions were dried over Na2SO4, filtered, and
concentrated in vacuo. The product was purified by column chromatography (SiO2, 5–15% EtOAc
in hexanes) to yield indole 5 (120 mg, 0.500 mmol, 99% yield over 2 steps) as a yellow oil; Rf =
0.54 (20% EtOAc in hexanes); 1H NMR (500 MHz, CDCl3) δ 9.75 (s, 1H), 7.66 (dt, J = 8.1, 1.0
Hz, 1H), 7.49 (dt, J = 8.4, 0.9 Hz, 1H), 7.38 (ddd, J = 8.3, 7.0, 1.1 Hz, 1H), 7.16 (ddd, J = 8.0, 6.9,
1.0 Hz, 1H), 5.87 (ddt, J = 16.6, 10.4, 7.4 Hz, 1H), 5.15 – 5.10 (m, 2H), 3.10 – 2.98 (m, 2H), 2.57
(dd, J = 13.8, 7.2 Hz, 1H), 2.38 (ddt, J = 13.8, 7.5, 1.2 Hz, 1H), 2.24 (ddd, J = 13.6, 7.1, 5.2 Hz,
1H), 2.05 (ddd, J = 13.6, 6.9, 5.2 Hz, 1H), 1.29 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 196.3,
138.7, 134.4, 130.3, 128.0, 126.9, 125.9, 121.4, 120.4, 118.3, 112.9, 45.5, 41.5, 35.7, 22.1, 18.4;
IR (Neat Film, NaCl): 3279, 3076, 2963, 2926, 1638, 1573, 1545, 1473, 1331, 1224, 1014, 992,
977, 916 cm-1; HRMS (ESI-APCI) m/z: [M+H]+ calc’d for C16H18NO 240.1383; Found 240.1383;
[α]25 –131.65 (c 7.84, CHCl3).
OMeH
N
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S30
Ethyl (S)-6-allyl-1-(4-methoxyphenyl)-6-methyl-7-oxo-4,5,6,7-tetrahydro-1H-indazole-3-
carboxylate (6)
Enaminone 2a (31 mg, 0.13 mmol, 1.0 equiv) and ethyl (Z)-2-chloro-2-(2-(4-
methoxyphenyl)hydrazono)acetate9 (73, 50 mg, 0.19 mmol, 1.5 equiv) were dissolved in toluene
(1.4 mL). Then, triethylamine (0.15 mL, 0.11 mmol, 0.83 equiv) was added. The reaction mixture
was heated at the reflux for 17 h. The reaction mixture was then cooled to ambient temperature,
quenched with water, and extracted with ethyl acetate. The organic layer was washed with brine
and dried over Na2SO4, filtered, and concentrated in vacuo. The product was purified by flash
column chromatography (5–15% EtOAc/hexanes) to give the compound 6 as a yellow-orange oil
(22 mg, , 6.0 µmol, 46% yield); 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J = 8.9 Hz, 2H), 6.94 (d, J
= 8.9 Hz, 2H), 5.80 – 5.72 (m, 1H), 5.12 – 5.05 (m, 2H), 4.44 (q, J = 7.1 Hz, 2H), 3.85 (s, 3H),
3.18 – 3.06 (m, 2H), 2.42 (ddt, J = 13.8, 7.1, 1.2 Hz, 1H), 2.27 (ddt, J = 13.7, 7.6, 1.1 Hz, 1H),
2.13 (ddd, J = 14.0, 6.6, 5.4 Hz, 1H), 1.98 (ddd, J = 14.0, 7.3, 5.6 Hz, 1H), 1.42 (t, J = 7.1 Hz,
3H), 1.17 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 192.7, 162.3, 160.1, 140.0, 135.2, 133.6, 132.9,
132.8, 127.1, 118.8, 113.8, 61.3, 55.7, 46.7, 40.8, 34.9, 21.6, 19.0, 14.6; IR (Neat Film, NaCl):
2917, 2357, 2340, 1691, 1515, 1301, 1251, 1195, 1127, 1026, 935 cm-1; HRMS (ESI-APCI) m/z:
[M+H]+ calc’d for C21H25N2O4 369.1809; Found 369.1791; [α]25 –7.56 (c 0.45, CHCl3).
(S)-6-allyl-3-bromo-6-methyl-2-morpholinocyclohex-2-en-1-one (SI4)
Enaminone 2a (120 mg, 0.51 mmol, 1.0 equiv) was dissolved in CH2Cl2 (4.5 mL, 0.1 M). The
reaction mixture was cooled to –78 °C. A solution of NBS (91 mg, 0.51 mmol, 1.0 equiv) in
CH2Cl2 (4.5 mL) was added dropwise to the reaction by syringe. The reaction mixture was stirred
OMe
NN
EtO2C
MeO
OMe
NO
Br
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S31
at –78 °C for 25 min. The solution was quenched with a solution of 10% K2CO3 (3 mL). The
mixture was warmed to room temperature and extracted with 3 x CH2Cl2. The organic layers were
combined, dried, filtered and concentrated. The residue was purified by flash column
chromatography (3% EtOAc/hexanes) to give the desired compound as a yellow oil (96 mg, 0.31
mmol, 60% yield). 1H NMR (500 MHz, CDCl3) δ 5.68 (ddt, J = 16.7, 10.2, 7.4 Hz, 1H), 5.10 –
5.01 (m, 2H), 3.71 (ddd, J = 5.3, 3.8, 1.3 Hz, 4H), 3.06 – 2.99 (m, 2H), 2.97 – 2.92 (m, 2H), 2.93
– 2.83 (m, 2H), 2.28 (ddt, J = 13.8, 7.3, 1.2 Hz, 1H), 2.21 (ddt, J = 13.8, 7.5, 1.2 Hz, 1H), 1.88
(ddd, J = 13.8, 6.3, 5.7 Hz, 1H), 1.74 (ddd, J = 13.9, 7.2, 5.8 Hz, 1H), 1.07 (s, 3H); 13C NMR (125
MHz, CDCl3) δ 199.4, 143.8, 141.9, 133.5, 118.7, 67.7, 50.2, 45.8, 40.9, 33.7, 33.3, 21.5; IR (Neat
Film, NaCl) 2958, 2851, 1678, 1606, 1451, 1261, 1212, 1113, 1049, 920 cm-1; HRMS (ESI-APCI)
m/z: [M+H]+ calc’d for C14H21BrNO2 314.0750; Found 314.0742; [α]25 –1.56 (c 1.68, CHCl3).
(S)-4-allyl-4-methyl-2-morpholino-5,6-dihydro-[1,1'-biphenyl]-3(4H)-one (7)
Compound SI4 (54 mg, 0.17 mmol, 1.0 equiv) was dissolved in DME (7 mL) and 1 M K3PO4
(0.72 mL, 4.5 equiv). Phenylboronic acid (29 mg, 0.24 mmol, 1.5 equiv) and PdCl2(dppf) (26 mg,
32 µmol, 0.19 equiv) were added to the reaction mixture. The mixture was heated to 60 °C under
nitrogen for 2h. The reaction mixture was cooled to room temperature and then extracted with
diethyl ether (3x). The combined organic layer was dried with Na2SO4, filtered and concentrated
in vacuo. The reaction mixture was purified by flash column chromatography (SiO2, 3–6%
EtOAc/hexanes) to give the product as bright yellow-orange oil (51 mg, 0.16 mmol, 96% yield). 1H NMR (500 MHz, CDCl3) δ 7.40 – 7.36 (m, 2H), 7.33 – 7.29 (m, 1H), 7.26 – 7.22 (m, 2H), 6.93
– 6.82 (m, 1H), 5.79 (ddt, J = 16.6, 10.3, 7.4 Hz, 1H), 5.11 – 5.05 (m, 2H), 3.53 (t, J = 4.6 Hz,
4H), 2.73 – 2.61 (m, 6H), 2.40 – 2.29 (m, 2H), 1.96 (dt, J = 13.7, 5.8 Hz, 1H), 1.85 (ddd, J = 13.5,
6.9, 6.1 Hz, 1H), 1.15 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 202.7, 145.7, 141.2, 140.5, 134.2,
129.8, 128.2, 127.9, 118.2, 115.4, 67.5, 51.2, 44.8, 41.4, 32.2, 29.0, 21.9; IR (Neat Film, NaCl):
2916, 2850, 2358, 1669, 1457, 1374, 1261, 1210, 1112, 1029, 978, 757, 698 cm-1; HRMS (ESI-
APCI) m/z: [M+H]+ calc’d for C20H26NO2 312.1958; Found 312.1968; [α]25 0.00 (c 0.76, CHCl3).
OMe
NO
Ph
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S32
References 1) Pangborn, A. M.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Safe and
Convenient Procedure for Solvent Purification. Organometallics 1996, 15, 1518–1520.
2) (a) Tani, K.; Behenna, D. C.; McFadden, R. M.; Stoltz, B. M. Org. Lett. 2007, 9, 2529–
2531. (b) Krout, M. R.; Mohr, J. T.; Stoltz, B. M. Org. Synth. 2009, 86, 181–193.
3) Tobias, M. A.; Strong, J. G.; Napier, R. P. J. Org. Chem. 1970, 35, 1709–1711.
4) Di-methyl ref
5) Prepared from 2-iodocyclohexenone and cyclohexylmagnesium bromide following the
procedure from the following publication: Barriault, L.; Thomas, J. D. O.; Clément, R. J.
Org. Chem. 2003, 68, 2317–2323.
6) Sato, K.; Inoue, S.; Kitagawa, T.; Takahashi, T. J. Org. Chem. 1973, 38, 551–554.
7) White, D. E.; Stewart, I. C.; Grubbs, R. H.; Stoltz, B. M. J. Am Chem. Soc. 2008, 130,
810–811.
8) Ghosh, S.; Chaudhuri, S.; Bisai, A. Chem. Eur. J. 2015, 21, 17479–17484.
9) Pinto, D. J. P.; Orwat, M. J.; Koch, S.; Rossi, K. A.; Alexander, R. S.; Smallwood, A.;
Wong, P. C.; Rendina, A. R.; Luettgen, J. M.; Knabbs, R. M.; He, K.; Xin, B.; Wexler, R.
R.; Lam, P. Y. S. J. Med. Chem. 2007, 50, 5339–5356.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S33
01
23
45
67
89
10
ppm
3.12
1.09
1.08
1.08
1.01
2.06
2.09
2.05
2.06
2.14
0.99
1.00
1.93
1.37
1.82
1.83
1.83
1.84
1.85
1.85
1.86
1.87
2.38
2.39
2.42
2.43
2.43
2.46
2.46
2.47
2.51
2.55
2.55
2.56
2.56
2.58
2.96
2.99
3.74
3.76
3.76
3.77
3.77
3.78
3.79
3.80
3.80
3.81
3.81
3.82
3.82
4.55
4.56
4.56
4.56
4.57
4.57
4.57
4.58
4.58
4.58
4.59
5.20
5.20
5.20
5.21
5.22
5.22
5.22
5.25
5.25
5.28
5.28
5.29
5.29
5.79
5.80
5.81
5.81
5.82
5.82
5.83
5.83
5.85
ON
O
1a
Me
O
O
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1a
.
Spectral Data for New Compounds
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S34
020406080100120140160180200220
ppm
20.6
22.7
33.3
50.0
54.2
66.0
66.9
118.9
124.0
131.6
146.4
172.4
193.9
Infrared spectrum (Thin Film, NaCl) of compound 1a.
13C NMR (125 MHz, CDCl3) of compound 1a.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S35
01
23
45
67
89
10
ppm
3.01
1.14
1.08
1.14
2.03
3.04
2.02
2.00
2.00
2.01
0.99
1.00
1.06
1.00
0.90
0.92
0.93
1.76
1.78
1.79
1.80
1.84
1.85
1.86
1.86
1.88
1.89
1.93
1.95
1.96
1.97
2.39
2.40
2.40
2.40
2.41
2.41
2.53
2.54
2.54
2.55
2.55
2.56
2.56
2.57
2.58
2.93
2.94
2.94
2.95
2.95
2.96
2.97
2.97
3.73
3.74
3.75
3.75
3.76
3.76
3.77
3.77
3.78
3.79
3.80
3.80
3.81
3.81
3.82
3.83
5.20
5.20
5.21
5.22
5.22
5.22
5.25
5.26
5.29
5.29
5.29
5.80
5.82
5.84
5.86
1 H N
MR
(400
MH
z, C
DC
l 3) o
f com
poun
d 1b
.
ON
O
1b
EtO
O
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S36
020406080100120140160180200220
ppm
9.1
22.6
27.0
29.8
50.0
57.9
65.8
67.0
119.0
123.5
131.7
146.8
171.3
193.6
Infrared spectrum (Thin Film, NaCl) of compound 1b.
13C NMR (100 MHz, CDCl3) of compound 1b.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S37
01
23
45
67
89
10
ppm
2.89
2.95
9.19
1.00
1.04
1.02
3.05
1.99
4.11
1.01
1.01
1.01
1.03
0.96
0.99
1.96
0.03
0.03
0.85
2.03
2.60
2.60
2.61
2.61
2.62
2.62
2.63
2.63
2.63
2.63
2.86
2.87
2.87
2.88
2.88
2.89
2.90
3.74
3.76
3.76
3.77
3.77
3.78
3.78
3.78
3.79
3.80
3.80
3.81
3.87
3.89
4.07
4.09
4.55
4.55
4.55
4.56
4.56
4.56
4.58
4.58
4.58
4.59
4.59
4.59
5.19
5.19
5.21
5.21
5.22
5.26
5.26
5.29
5.29
5.81
5.82
5.82
5.82
5.82
5.83
5.83
5.83
5.83
5.83
5.84
5.84
5.87
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1c
.
O
O
ON
O
1cOTBS
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S38
020406080100120140160180200220
ppm
-5.5
-5.5
18.3
22.4
25.9
25.9
25.9
28.0
50.0
59.9
65.4
66.0
66.9
118.8
125.0
131.8
146.7
169.6
192.0
Infrared spectrum (Thin Film, NaCl) of compound 1c.
13C NMR (100 MHz, CDCl3) of compound 1c.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S39
01
23
45
67
89
10
ppm
6.00
9.07
2.05
1.05
1.03
4.01
1.99
6.02
2.00
0.98
0.99
0.91
1.04
0.02
0.86
1.92
1.93
1.94
1.94
1.94
1.95
1.96
1.97
1.98
2.12
2.13
2.13
2.14
2.16
2.16
2.53
2.54
2.55
2.55
2.55
2.56
2.56
2.57
2.58
2.58
2.93
2.94
2.94
3.68
3.69
3.69
3.71
3.72
3.73
3.73
3.74
3.75
3.75
3.75
3.76
3.77
3.77
3.78
3.79
3.80
3.80
3.80
4.55
4.55
4.55
4.56
4.56
4.56
4.56
4.57
4.57
4.58
5.20
5.20
5.22
5.22
5.26
5.26
5.29
5.29
5.80
5.82
5.84
5.86
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1d
.
O
O
ON
O
1dOTBS
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S40
020406080100120140160180200220
ppm
-5.2
18.4
22.7
26.0
30.8
36.8
50.0
56.5
59.7
66.0
66.9
119.1
123.7
131.7
146.5
171.0
193.3
Infrared spectrum (Thin Film, NaCl) of compound 1d.
13C NMR (100 MHz, CDCl3) of compound 1d.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S41
01
23
45
67
89
10
ppm
1.09
1.06
1.07
3.04
4.07
2.00
3.00
2.00
2.01
1.99
0.95
0.97
0.98
0.93
2.05
2.06
2.07
2.16
2.17
2.18
2.31
2.32
2.33
2.34
2.37
2.38
2.39
2.41
2.43
2.45
2.50
2.51
2.51
2.52
2.52
2.53
2.54
2.54
2.90
2.91
2.91
2.92
2.92
2.93
2.94
2.94
3.62
3.70
3.71
3.71
3.72
3.73
3.73
3.74
3.75
3.75
3.76
3.76
3.78
4.52
4.53
4.53
4.53
4.54
4.54
4.54
4.55
4.55
4.56
5.18
5.18
5.20
5.20
5.23
5.23
5.27
5.27
5.69
5.70
5.70
5.71
5.71
5.77
5.79
5.80
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1e
.
O
O
ON
O
1eCO
2Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S42
020406080100120140160180200220
ppm
22.5
28.9
29.5
30.7
49.8
51.7
56.7
66.1
66.8
66.8
119.2
123.3
131.4
146.6
170.9
173.4
193.1
Infrared spectrum (Thin Film, NaCl) of compound 1e.
13C NMR (100 MHz, CDCl3) of compound 1e.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S43
01
23
45
67
89
10
ppm
1.12
1.13
4.02
1.00
1.05
2.01
2.09
1.03
2.00
2.04
2.05
2.05
0.99
1.01
1.02
1.00
1.86
1.98
2.00
2.01
2.07
2.08
2.09
2.10
2.34
2.35
2.35
2.37
2.37
2.37
2.38
2.46
2.47
2.48
2.51
2.51
2.51
2.52
2.53
2.53
2.53
2.54
2.54
2.54
2.55
2.55
2.92
2.92
2.93
2.93
3.71
3.72
3.72
3.73
3.74
3.74
3.75
3.76
3.77
3.77
3.78
4.53
4.53
4.54
4.54
4.54
4.55
4.55
4.56
4.56
4.56
5.19
5.19
5.21
5.21
5.24
5.24
5.28
5.28
5.71
5.72
5.72
5.73
5.78
5.80
5.82
5.84
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1f
.
O
O
ON
O
1fMeO
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S44
020406080100120140160180200220
ppm
22.6
27.7
30.0
30.0
31.1
38.9
49.9
49.9
56.7
66.0
66.9
119.3
123.5
131.4
146.7
171.2
193.4
207.7
Infrared spectrum (Thin Film, NaCl) of compound 1f.
13C NMR (100 MHz, CDCl3) of compound 1f.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S45
01
23
45
67
89
10
ppm
1.00
1.05
1.07
3.02
4.06
2.00
1.97
1.99
2.00
0.95
0.98
0.98
1.00
1.90
2.07
2.08
2.09
2.10
2.19
2.20
2.21
2.38
2.39
2.40
2.40
2.42
2.42
2.42
2.43
2.44
2.45
2.52
2.52
2.53
2.53
2.54
2.54
2.55
2.56
2.57
2.57
2.93
2.94
2.94
2.95
2.95
2.96
2.97
2.97
3.72
3.73
3.74
3.74
3.75
3.75
3.77
3.77
3.78
3.79
3.79
3.80
3.80
4.58
4.59
4.59
4.60
4.60
4.60
4.61
4.61
4.61
5.23
5.24
5.25
5.26
5.27
5.27
5.31
5.31
5.76
5.80
5.82
5.83
5.85
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1g
.
O
O
ON
O
1gCN
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S46
020406080100120140160180200220
ppm
13.3
22.5
30.2
31.1
49.8
56.5
66.5
66.8
119.4
119.9
123.7
131.1
146.6
170.2
192.7
Infrared spectrum (Thin Film, NaCl) of compound 1g.
13C NMR (125 MHz, CDCl3) of compound 1g.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S47
01
23
45
67
89
10
ppm
1.02
2.01
2.99
1.95
1.01
1.00
1.97
2.00
1.98
0.94
0.97
0.98
0.94
2.01
2.99
2.34
2.35
2.35
2.35
2.51
2.51
2.52
2.52
2.53
2.53
2.54
2.54
2.55
2.95
2.95
2.96
2.96
2.97
2.98
3.13
3.15
3.24
3.27
3.74
3.75
3.76
3.76
3.77
3.77
3.78
3.79
3.80
3.81
3.82
3.82
3.83
3.83
3.84
3.85
5.20
5.20
5.22
5.22
5.24
5.24
5.27
5.28
5.71
5.71
5.72
5.72
5.76
5.78
5.79
5.82
7.16
7.16
7.16
7.17
7.17
7.18
7.20
7.21
7.22
7.22
7.23
7.23
7.23
7.24
7.24
7.25
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1h
.
O
O
ON
O
1h
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S48
020406080100120140160180200220
ppm
22.7
30.0
39.7
49.9
58.7
66.1
66.9
119.2
123.9
126.9
128.2
130.7
131.5
136.4
146.8
170.5
170.5
192.6
Infrared spectrum (Thin Film, NaCl) of compound 1h.
13C NMR (100 MHz, CDCl3) of compound 1h.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S49
01
23
45
67
89
10
ppm
1.00
2.04
3.00
2.00
1.02
1.02
5.08
2.04
2.03
0.98
1.10
0.95
1.01
2.07
2.01
2.33
2.33
2.34
2.34
2.34
2.35
2.35
2.36
2.36
2.51
2.52
2.52
2.52
2.53
2.54
2.54
2.55
2.55
2.95
2.95
2.96
2.96
2.97
2.98
3.08
3.11
3.17
3.20
3.75
3.75
3.76
3.77
3.77
3.77
3.78
3.79
3.80
3.81
3.82
3.82
3.83
3.83
3.84
4.52
4.52
4.52
4.52
4.53
4.53
4.53
4.54
5.20
5.21
5.21
5.22
5.23
5.23
5.24
5.25
5.28
5.28
5.28
5.72
5.77
5.79
5.81
5.83
6.77
6.79
7.08
7.10
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1i
.
O
O
ON
O
1i
OMe
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S50
020406080100120140160180200220
ppm
22.7
30.0
38.9
50.0
55.3
58.8
66.1
66.9
113.6
119.2
123.9
128.3
131.6
131.7
146.9
158.6
170.6
192.7
Infrared spectrum (Thin Film, NaCl) of compound 1i.
13C NMR (100 MHz, CDCl3) of compound 1i.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S51
01
23
45
67
89
10
ppm
1.00
2.03
3.04
2.00
1.01
1.03
2.03
2.05
2.03
2.01
1.95
2.04
2.11
2.34
2.35
2.36
2.37
2.37
2.38
2.38
2.38
2.51
2.51
2.52
2.52
2.52
2.53
2.53
2.54
2.54
2.55
2.96
2.96
2.97
2.97
2.98
2.99
2.99
3.18
3.20
3.27
3.30
3.75
3.75
3.76
3.76
3.77
3.77
3.78
3.79
3.81
3.81
3.82
3.83
3.83
3.84
3.84
4.50
4.50
4.50
4.51
4.51
4.51
4.52
4.52
5.20
5.20
5.20
5.21
5.22
5.22
5.22
5.23
5.25
5.25
5.25
5.72
7.31
7.33
7.33
7.49
7.50
7.50
7.51
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1j
.
O
O
ON
O
1j
CF3
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S52
020406080100120140160180200220
ppm
22.7
30.4
39.6
49.9
58.7
66.3
66.9
119.5
123.3
123.8
125.0
125.1
125.1
125.1
128.8
129.1
129.3
129.6
131.2
131.2
140.7
146.8
170.3
192.4
Infrared spectrum (Thin Film, NaCl) of compound 1j.
13C NMR (125 MHz, CDCl3) of compound 1j.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S53
-180-160-140-120-100-80-60-40-20020
ppm
-62.5
19F NMR (470 MHz, CDCl3) of compound 1j.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S54
01
23
45
67
89
10
ppm
2.99
2.92
1.00
1.02
1.01
3.04
2.00
2.03
2.01
2.06
2.02
1.04
1.41
1.71
1.72
1.84
1.86
1.86
1.87
1.88
1.88
1.89
1.90
2.41
2.41
2.45
2.46
2.46
2.46
2.48
2.49
2.49
2.49
2.52
2.53
2.56
2.57
2.57
2.58
2.59
2.59
2.60
2.60
2.60
2.61
2.98
2.98
2.99
2.99
3.00
3.00
3.01
3.02
3.02
3.75
3.75
3.76
3.77
3.77
3.78
3.78
3.79
3.80
3.81
3.82
3.82
3.83
3.83
3.84
3.84
4.51
4.52
4.52
4.52
4.91
4.93
5.78
5.78
5.79
5.79
5.79
5.80
5.80
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1k
.
O
O
ON
O
1k
Me
Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S55
020406080100120140160180200220
ppm
19.5
20.6
22.6
33.3
49.8
54.1
66.8
68.4
113.5
123.9
139.4
146.3
172.3
193.7
Infrared spectrum (Thin Film, NaCl) of compound 1k.
13C NMR (125 MHz, CDCl3) of compound 1k.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S56
01
23
45
67
89
10
ppm
3.01
1.03
1.01
1.04
3.04
2.00
2.06
2.07
1.05
0.99
1.02
1.01
1.01
1.43
1.89
1.90
1.91
2.43
2.47
2.59
2.59
2.60
2.60
2.61
2.61
2.61
2.61
2.62
2.63
2.63
2.98
2.98
2.99
2.99
3.01
3.01
3.75
3.76
3.77
3.77
3.78
3.78
3.79
3.80
3.80
3.81
3.82
3.82
3.83
3.83
3.84
3.85
4.62
4.62
4.62
4.62
4.64
4.65
4.65
4.65
4.65
4.70
4.71
4.71
4.71
4.73
4.73
4.73
4.73
5.40
5.40
5.44
5.44
5.44
5.44
5.45
5.45
5.81
5.81
5.81
5.82
5.82
5.83
5.83
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1l
.
O
O
ON
O
1l
Me
Cl
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S57
020406080100120140160180200220
ppm
20.6
22.6
33.3
49.9
54.2
66.7
66.9
115.7
115.8
124.3
135.4
146.3
171.9
193.5
Infrared spectrum (Thin Film, NaCl) of compound 1l.
13C NMR (125 MHz, CDCl3) of compound 1l.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S58
01
23
45
67
89
10
ppm
3.02
2.06
3.99
1.07
1.07
1.05
3.07
2.00
2.00
0.99
1.06
1.00
1.00
1.37
1.48
1.48
1.49
1.51
1.61
1.61
1.62
1.62
1.63
1.63
1.63
1.64
1.64
1.64
1.64
1.65
1.65
1.65
1.66
1.66
1.67
1.67
1.68
1.81
1.82
1.82
1.83
1.84
1.84
1.85
2.37
2.42
2.48
2.48
2.49
2.49
2.49
2.50
2.50
2.51
2.51
2.52
2.52
2.85
2.86
2.87
2.88
4.55
4.56
4.56
4.56
4.57
4.57
4.57
4.57
4.58
5.19
5.19
5.21
5.21
5.21
5.25
5.25
5.28
5.29
5.73
5.73
5.74
5.74
5.74
5.75
5.80
5.82
5.84
5.86
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1m
.
O
OMeO
N
1m
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S59
020406080100120140160180200220
ppm
20.7
22.8
24.5
26.0
33.4
51.0
54.2
65.8
118.7
123.5
131.8
147.7
172.6
194.3
Infrared spectrum (Thin Film, NaCl) of compound 1m.
13C NMR (125 MHz, CDCl3) of compound 1m.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S60
01
23
45
67
89
10
ppm
3.00
1.09
3.10
1.07
1.06
1.11
2.01
2.09
4.10
1.00
1.01
0.95
0.97
0.95
1.33
1.76
1.77
1.78
1.78
1.79
1.80
1.80
1.82
1.95
1.95
1.96
2.30
2.30
2.30
2.31
2.36
2.37
2.37
2.38
2.39
2.39
2.40
2.40
2.84
2.86
2.87
2.87
2.87
2.92
2.92
2.93
2.95
3.65
3.65
3.66
3.66
3.66
3.67
3.68
4.53
4.53
4.54
4.54
4.55
4.55
4.56
4.56
4.57
4.57
4.58
4.58
5.17
5.17
5.17
5.19
5.19
5.19
5.19
5.22
5.22
5.25
5.25
5.26
5.26
5.79
5.80
5.80
5.81
5.82
5.84
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1n
.
O
O
ON
O
1n
Me
Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S61
020406080100120140160180200220
ppm
19.6
20.5
29.2
32.3
50.3
53.9
65.7
67.9
118.4
131.8
142.1
153.2
172.5
194.8
Infrared spectrum (Thin Film, NaCl) of compound 1n.
13C NMR (125 MHz, CDCl3) of compound 1n.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S62
01
23
45
67
89
10
ppm
1.09
2.30
2.09
3.01
6.08
1.23
1.13
3.15
2.01
1.00
1.04
0.95
1.00
0.96
1.07
1.08
1.10
1.10
1.12
1.13
1.15
1.32
1.32
1.34
1.35
1.37
1.62
1.62
1.65
1.65
1.67
1.69
1.69
1.69
1.70
1.70
1.70
1.70
1.71
1.71
1.72
1.72
1.72
1.73
1.73
1.75
1.75
1.76
1.84
1.85
1.86
2.33
2.45
2.46
2.47
2.47
2.48
2.48
2.53
2.54
4.56
4.56
4.56
4.57
4.57
4.58
4.58
4.58
4.59
5.19
5.19
5.21
5.21
5.25
5.25
5.28
5.28
5.82
5.84
5.85
6.50
6.50
6.51
6.51
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1o
.
O
O
O
1o
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S63
020406080100120140160180200220
ppm
20.6
23.6
26.5
26.8
26.9
32.3
32.8
33.4
36.8
53.6
65.8
118.5
131.9
140.9
144.2
172.8
196.8
Infrared spectrum (Thin Film, NaCl) of compound 1o.
13C NMR (125 MHz, CDCl3) of compound 1o.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S64
01
23
45
67
89
10
ppm
3.00
1.00
3.00
2.01
4.01
2.03
1.02
1.08
1.03
1.00
1.42
2.36
2.36
2.39
2.40
3.01
3.01
3.01
3.02
3.03
3.04
3.05
3.15
3.16
3.16
3.16
3.17
3.17
3.18
3.19
3.19
3.78
3.78
3.79
3.79
3.79
3.80
3.80
4.57
4.57
4.58
4.58
4.58
4.59
5.19
5.19
5.20
5.20
5.21
5.21
5.22
5.22
5.25
5.25
5.25
5.26
5.28
5.29
5.29
5.29
5.81
5.82
5.83
5.83
5.83
5.84
5.85
5.86
5.86
5.87
5.87
5.87
5.88
5.89
6.39
6.39
6.40
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 1p
.
O
NO
OO
1p
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S65
020406080100120140160180200220
ppm
21.1
37.8
48.5
54.1
65.9
66.6
118.3
131.8
131.9
148.6
171.6
201.8
Infrared spectrum (Thin Film, NaCl) of compound 1p.
13C NMR (125 MHz, CDCl3) of compound 1p.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S66
01
23
45
67
89
10
ppm
3.01
1.01
1.03
1.01
1.02
2.00
2.00
2.01
4.04
2.00
0.97
1.00
1.09
1.09
1.71
1.72
1.73
1.74
1.74
1.75
1.85
1.86
1.88
1.89
2.20
2.22
2.23
2.23
2.24
2.25
2.32
2.32
2.33
2.33
2.35
2.36
2.40
2.41
2.41
2.42
2.42
2.42
2.42
2.43
2.43
2.44
2.44
2.69
2.70
2.71
2.71
2.71
2.72
2.80
2.81
2.82
2.84
2.85
3.79
3.79
3.80
3.80
3.81
3.81
3.81
5.03
5.03
5.04
5.05
5.05
5.05
5.06
5.06
5.06
5.06
5.71
5.73
5.73
5.74
5.74
5.87
5.88
5.89
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2a
.
OMe
NO
2a
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S67
020406080100120140160180200220
ppm
21.8
21.9
33.2
41.2
45.4
50.5
66.9
118.1
125.0
134.0
145.5
200.4
Infrared spectrum (Thin Film, NaCl) of compound 2a.
13C NMR (125 MHz, CDCl3) of compound 2a.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S68
01
23
45
67
89
10
ppm
3.01
2.00
2.00
1.00
1.00
2.00
2.01
2.00
4.00
0.98
1.00
1.00
1.00
0.79
0.80
0.82
1.56
1.56
1.58
1.58
1.59
1.60
1.61
1.61
1.80
1.81
1.82
2.20
2.22
2.23
2.23
2.23
2.25
2.25
2.25
2.32
2.32
2.33
2.33
2.34
2.36
2.38
2.39
2.39
2.40
2.40
2.41
2.41
2.41
2.42
2.42
2.69
2.70
2.70
2.71
2.71
2.72
2.75
2.76
2.76
2.77
2.77
2.78
3.77
3.77
3.78
3.78
3.78
3.79
3.79
4.99
5.00
5.00
5.00
5.00
5.01
5.01
5.02
5.03
5.03
5.03
5.82
5.83
5.84
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2b
.
OEt
NO
2b
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S69
020406080100120140160180200220
ppm
8.4
21.8
27.0
30.4
38.8
48.6
50.6
67.0
117.9
124.8
134.4
146.0
200.2
Infrared spectrum (Thin Film, NaCl) of compound 2b.
13C NMR (125 MHz, CDCl3) of compound 2b.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S70
01
23
45
67
89
10
ppm
2.83
2.92
9.00
1.01
1.00
1.00
3.05
4.00
1.01
1.04
3.92
2.00
0.98
0.94
0.01
0.01
0.85
1.88
1.89
1.90
1.92
1.93
1.95
1.95
1.96
1.98
2.24
2.25
2.26
2.26
2.27
2.27
2.28
2.28
2.28
2.38
2.39
2.39
2.40
2.40
2.40
2.41
2.41
2.41
2.42
2.42
2.42
2.43
2.43
2.43
2.43
2.73
2.74
2.75
3.61
3.63
3.67
3.69
3.78
3.79
3.79
5.00
5.00
5.00
5.00
5.01
5.01
5.02
5.03
5.03
5.03
5.03
5.04
5.04
5.67
5.68
5.69
5.69
5.69
5.71
5.73
5.73
5.86
5.87
5.88
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2c
.
ON
O
2c
OTBS
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S71
020406080100120140160180200220
ppm
-5.5
-5.5
-5.5
18.3
21.7
25.9
25.9
28.5
37.2
50.5
51.0
66.1
67.0
118.0
125.1
134.1
146.5
198.8
Infrared spectrum (Thin Film, NaCl) of compound 2c.
13C NMR (125 MHz, CDCl3) of compound 2c.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S72
01
23
45
67
89
10
ppm
2.78
2.87
9.04
1.00
3.01
1.00
3.00
3.93
0.99
1.03
4.01
2.00
1.00
0.94
0.02
0.03
0.87
1.75
1.77
1.77
1.78
1.83
1.84
1.84
1.85
1.85
1.86
1.87
1.87
1.87
1.88
1.88
1.88
1.89
1.89
2.27
2.28
2.28
2.29
2.30
2.36
2.37
2.39
2.40
2.42
2.43
2.43
2.44
2.44
2.44
2.45
2.45
2.75
2.76
2.77
3.56
3.56
3.56
3.57
3.58
3.58
3.59
3.67
3.68
3.69
3.69
3.70
3.70
3.71
3.79
3.80
3.81
5.02
5.02
5.03
5.04
5.04
5.04
5.05
5.06
5.06
5.06
5.06
5.07
5.86
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2d
.
ON
O
2d
OTBS
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S73
020406080100120140160180200220
ppm
-5.2
-5.1
18.4
21.9
26.1
31.3
37.0
39.5
47.8
50.6
59.5
67.0
118.3
125.0
134.2
145.8
199.7
Infrared spectrum (Thin Film, NaCl) of compound 2d.
13C NMR (125 MHz, CDCl3) of compound 2d.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S74
01
23
45
67
89
10
ppm
3.04
1.11
2.09
2.05
2.07
4.03
3.05
4.00
2.02
1.01
1.00
1.80
1.80
1.81
1.81
1.82
1.82
1.83
1.83
1.83
1.85
1.85
1.86
1.86
1.92
1.93
1.94
2.19
2.19
2.21
2.21
2.22
2.24
2.25
2.26
2.29
2.30
2.30
2.30
2.30
2.31
2.31
2.31
2.32
2.32
2.33
2.33
2.42
2.42
2.43
2.43
2.44
2.44
2.45
2.72
2.73
2.74
2.75
3.63
3.63
3.76
3.77
3.77
3.78
3.78
3.78
5.02
5.03
5.03
5.03
5.04
5.05
5.05
5.05
5.06
5.06
5.07
5.07
5.07
5.85
5.86
5.87
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2e
.
ON
O
2e
OMe
O
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S75
020406080100120140160180200220
ppm
21.6
28.8
29.2
30.6
38.9
47.8
50.4
51.6
66.8
118.6
125.0
133.3
145.7
174.0
199.1
Infrared spectrum (Thin Film, NaCl) of compound 2e.
13C NMR (125 MHz, CDCl3) of compound 2e.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S76
01
23
45
67
89
10
ppm
4.13
3.00
1.06
2.04
3.11
2.01
2.00
4.01
2.00
1.00
0.99
1.78
1.79
1.79
1.80
1.80
1.81
1.81
1.82
1.83
1.83
1.83
1.84
1.85
1.86
1.86
2.12
2.24
2.25
2.25
2.25
2.26
2.27
2.27
2.31
2.31
2.31
2.32
2.32
2.32
2.33
2.35
2.35
2.36
2.43
2.44
2.44
2.45
2.45
2.46
2.46
2.47
2.47
2.69
2.70
2.71
2.72
2.73
2.76
2.77
2.78
2.78
2.79
3.78
3.79
3.80
5.04
5.04
5.05
5.06
5.06
5.06
5.07
5.07
5.08
5.08
5.67
5.69
5.70
5.88
5.89
5.89
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2f
.
ON
O
2f
Me
O
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S77
020406080100120140160180200220
ppm
21.8
28.0
30.2
31.0
38.4
39.3
47.9
50.7
67.0
118.7
125.5
133.6
145.9
199.6
208.6
Infrared spectrum (Thin Film, NaCl) of compound 2f.
13C NMR (125 MHz, CDCl3) of compound 2f.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S78
01
23
45
67
89
10
ppm
1.16
2.03
1.17
6.27
2.00
2.02
4.01
2.04
1.00
0.95
1.77
1.78
1.78
1.79
1.80
1.81
1.85
1.86
1.86
1.87
1.87
1.88
1.89
2.06
2.06
2.08
2.10
2.26
2.27
2.28
2.29
2.29
2.30
2.30
2.31
2.31
2.33
2.35
2.35
2.37
2.45
2.46
2.47
2.49
2.63
2.64
2.64
2.65
2.65
2.66
2.66
2.67
2.80
2.81
2.81
2.82
2.83
2.83
2.84
2.84
2.85
3.76
3.77
3.77
3.78
3.78
3.79
5.07
5.07
5.10
5.10
5.11
5.11
5.13
5.13
5.62
5.64
5.65
5.89
5.90
5.91
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2g
.
ON
O
2g
CN
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S79
020406080100120140160180200220
ppm
12.3
21.6
30.3
30.5
38.8
48.0
50.5
66.9
119.5
120.1
125.4
132.4
145.7
198.5
Infrared spectrum (Thin Film, NaCl) of compound 2g.
13C NMR (125 MHz, CDCl3) of compound 2g.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S80
01
23
45
67
89
10
ppm
1.05
1.10
1.13
3.01
5.01
1.05
4.01
2.05
1.00
0.97
1.99
3.00
1.72
1.73
1.74
1.75
1.79
1.80
1.82
2.13
2.15
2.16
2.18
2.40
2.41
2.41
2.42
2.42
2.42
2.43
2.43
2.43
2.44
2.44
2.44
2.46
2.71
2.73
2.74
2.74
2.75
2.75
2.76
2.77
3.06
3.09
3.79
3.80
3.81
3.81
5.03
5.03
5.06
5.06
5.07
5.07
5.07
5.07
5.09
5.09
5.09
5.76
5.78
5.87
5.88
5.89
7.11
7.12
7.12
7.13
7.13
7.13
7.19
7.20
7.20
7.20
7.22
7.22
7.22
7.23
7.24
7.24
7.25
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2h
.
OBn
NO
2h
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S81
020406080100120140160180200220
ppm
21.8
29.8
39.8
40.7
49.9
50.6
67.0
118.6
125.2
126.5
128.1
128.1
130.9
130.9
134.1
137.6
146.3
199.2
Infrared spectrum (Thin Film, NaCl) of compound 2h.
13C NMR (125 MHz, CDCl3) of compound 2h.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S82
01
23
45
67
89
10
ppm
1.07
1.02
1.00
3.00
1.02
4.00
1.00
2.98
3.98
2.00
0.95
0.99
1.92
2.00
1.70
1.71
1.71
1.73
1.74
1.77
1.78
1.79
1.81
2.11
2.12
2.13
2.13
2.14
2.15
2.15
2.15
2.40
2.40
2.41
2.41
2.41
2.42
2.42
2.43
2.43
2.43
2.44
2.45
2.65
2.68
2.74
2.75
2.76
2.77
2.77
2.99
3.02
3.77
3.79
3.80
3.81
5.01
5.02
5.02
5.05
5.05
5.05
5.06
5.06
5.06
5.06
5.08
5.08
5.08
5.08
5.75
5.76
5.77
5.77
5.86
5.87
5.88
6.77
6.77
6.78
6.79
7.03
7.03
7.04
7.04
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2i
.
ON
O
2i
OMe
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S83
020406080100120140160180200220
ppm
21.9
29.7
39.8
39.9
49.9
50.6
55.3
67.0
113.5
118.5
125.3
129.5
131.8
134.1
146.3
158.3
199.3
Infrared spectrum (Thin Film, NaCl) of compound 2i.
13C NMR (125 MHz, CDCl3) of compound 2i.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S84
01
23
45
67
89
10
ppm
1.07
1.06
1.03
3.05
2.90
1.99
1.00
3.87
0.95
1.00
0.97
0.93
2.01
1.91
1.70
1.71
1.71
1.73
1.77
1.78
1.79
1.81
2.20
2.21
2.22
2.23
2.24
2.37
2.38
2.38
2.39
2.39
2.39
2.40
2.40
2.41
2.41
2.41
2.42
2.42
2.44
2.45
2.69
2.70
2.71
2.71
2.72
2.72
2.74
2.77
2.78
2.78
2.79
2.80
2.80
3.19
3.21
3.80
3.80
3.80
3.81
3.81
3.81
3.82
5.06
5.07
5.10
5.10
5.11
5.12
5.12
5.13
5.14
5.14
5.76
5.78
5.78
5.87
5.88
5.89
7.25
7.26
7.26
7.48
7.49
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2j
.
ON
O
2j
CF3
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S85
020406080100120140160180200220
ppm
21.8
29.9
39.8
40.4
50.0
50.6
66.9
119.1
123.3
125.0
125.4
125.5
131.2
133.5
142.1
146.2
198.6
Infrared spectrum (Thin Film, NaCl) of compound 2j.
13C NMR (125 MHz, CDCl3) of compound 2j.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S86
-180-160-140-120-100-80-60-40-20020
ppm
-62.4
19F NMR (470 MHz, CDCl3) of compound 2j.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S87
01
23
45
67
89
10
ppm
3.00
2.97
1.00
1.00
1.00
2.00
1.00
2.01
1.99
4.07
1.02
1.03
1.01
1.10
1.66
1.68
1.69
1.70
1.71
1.88
1.88
1.90
1.90
1.91
1.91
2.16
2.16
2.19
2.19
2.41
2.42
2.42
2.42
2.42
2.43
2.43
2.43
2.44
2.44
2.44
2.50
2.50
2.52
2.53
2.63
2.63
2.64
2.64
2.65
2.66
2.66
2.66
2.89
2.90
2.90
2.91
2.91
2.92
2.93
3.77
3.78
3.78
3.79
3.80
3.80
3.80
3.80
3.81
3.82
3.82
3.83
4.64
4.65
4.65
4.65
4.65
4.65
4.82
4.82
4.82
4.82
5.88
5.89
5.90
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2k
.
OMe
NO
2k
Me
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S88
020406080100120140160180200220
ppm
21.9
23.3
24.7
33.3
44.9
44.9
45.6
50.5
67.0
115.0
115.0
115.0
125.0
142.4
145.6
200.3
Infrared spectrum (Thin Film, NaCl) of compound 2k.
13C NMR (125 MHz, CDCl3) of compound 2k.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S89
01
23
45
67
89
10
ppm
3.01
1.00
1.05
2.02
1.02
2.05
1.05
2.07
4.04
1.05
1.03
1.08
1.17
1.80
1.81
1.82
1.83
2.01
2.02
2.02
2.03
2.05
2.05
2.44
2.45
2.45
2.46
2.46
2.46
2.46
2.47
2.47
2.47
2.48
2.52
2.55
2.66
2.66
2.67
2.67
2.68
2.68
2.68
2.69
2.69
2.69
2.70
2.84
2.84
2.87
2.87
2.88
2.89
2.89
2.89
2.90
2.90
2.91
2.92
2.92
3.78
3.79
3.79
3.80
3.80
3.81
3.81
3.81
3.82
3.82
3.83
3.83
5.15
5.15
5.15
5.16
5.27
5.28
5.28
5.28
5.91
5.91
5.92
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2l
.
OMe
NO
2l
Cl
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S90
020406080100120140160180200220
ppm
21.8
22.5
32.8
45.6
46.1
50.5
67.0
116.7
125.1
138.9
145.6
199.1
Infrared spectrum (Thin Film, NaCl) of compound 2l.
13C NMR (125 MHz, CDCl3) of compound 2l.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S91
01
23
45
67
89
10
ppm
2.92
2.01
4.91
1.00
1.00
2.98
1.95
1.98
1.98
1.00
1.00
1.07
1.47
1.49
1.50
1.63
1.64
1.64
1.65
1.66
1.67
1.68
1.70
1.71
1.83
1.84
1.86
2.19
2.21
2.22
2.23
2.31
2.32
2.33
2.35
2.36
2.37
2.39
2.40
2.41
2.42
2.43
2.44
2.57
2.58
2.60
2.61
2.62
2.68
2.69
2.70
2.72
2.73
5.01
5.02
5.02
5.04
5.69
5.71
5.71
5.72
5.73
5.74
5.74
5.75
5.76
5.78
5.83
5.84
5.85
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2m
.
OMe
N
2m
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S92
020406080100120140160180200220
ppm
21.9
21.9
22.1
22.1
24.5
26.1
33.4
41.4
41.4
45.5
51.6
118.0
124.7
134.4
147.0
200.8
Infrared spectrum (Thin Film, NaCl) of compound 2m.
13C NMR (100 MHz, CDCl3) of compound 2m.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S93
01
23
45
67
89
10
ppm
3.01
1.02
1.01
3.01
1.01
1.01
2.00
4.00
4.10
2.00
0.96
1.03
1.65
1.66
1.67
1.67
1.68
1.68
1.70
1.79
1.80
1.80
1.82
1.82
1.83
1.83
1.99
2.18
2.19
2.19
2.20
2.20
2.24
2.25
2.26
2.26
2.26
2.34
2.34
2.35
2.35
2.35
2.36
2.36
2.36
2.36
2.37
2.37
2.37
2.37
2.38
2.89
2.90
2.91
2.91
2.92
2.93
3.67
3.68
3.69
5.01
5.01
5.01
5.02
5.03
5.04
5.04
5.04
5.04
5.04
5.05
5.05
5.05
5.06
5.06
5.06
5.69
5.71
5.71
5.72
5.72
5.74
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2n
.
OMe
NO
Me
2n
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S94
020406080100120140160180200220
ppm
19.76
21.82
28.66
32.46
41.29
44.93
50.64
68.07
118.03
134.34
141.60
153.45
202.05
Infrared spectrum (Thin Film, NaCl) of compound 2n.
13C NMR (125 MHz, CDCl3) of compound 2n.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S95
01
23
45
67
89
10
ppm
5.00
1.02
2.00
6.06
1.03
1.02
3.05
0.96
2.00
0.94
0.95
1.00
1.03
1.03
1.05
1.06
1.16
1.33
1.36
1.62
1.62
1.63
1.63
1.64
1.65
1.65
1.65
1.68
1.69
1.70
1.70
1.71
1.71
1.72
1.72
1.72
1.73
1.73
1.74
1.74
1.75
1.85
1.85
1.87
1.88
2.17
2.19
2.29
2.30
2.33
2.33
2.33
2.34
2.34
2.34
2.35
2.35
2.35
2.36
2.36
5.01
5.01
5.02
5.04
5.04
5.04
5.05
5.05
5.05
5.05
5.05
5.06
5.06
5.70
5.72
5.73
6.49
6.50
6.50
6.50
6.51
6.51
O 2o
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2o
.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S96
020406080100120140160180200220
ppm
22.0
23.0
26.5
26.9
26.9
32.7
33.0
33.3
36.4
41.4
44.4
117.9
134.6
140.5
143.4
203.2
Infrared spectrum (Thin Film, NaCl) of compound 2o.
13C NMR (100 MHz, CDCl3) of compound 2o.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S97
01
23
45
67
89
10
ppm
3.00
1.03
2.08
1.04
2.03
2.08
4.03
2.05
1.00
1.02
1.09
2.13
2.15
2.17
2.18
2.21
2.22
2.22
2.23
2.47
2.47
2.47
2.50
2.51
3.01
3.02
3.02
3.03
3.04
3.06
3.07
3.08
3.08
3.09
3.76
3.77
3.78
4.99
5.00
5.01
5.01
5.02
5.02
5.04
5.05
5.05
5.05
5.57
5.57
5.59
5.59
5.59
5.59
5.60
5.61
5.61
5.62
5.62
5.63
5.63
5.64
5.64
5.64
5.66
5.66
6.25
6.25
6.26
6.26
O
NO
2p
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 2p
.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S98
020406080100120140160180200220
ppm
24.0
37.2
42.7
42.7
46.8
48.6
66.7
118.2
131.6
133.9
149.3
209.1
Infrared spectrum (Thin Film, NaCl) of compound 2p.
13C NMR (125 MHz, CDCl3) of compound 2p.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S99
01
23
45
67
89
10
ppm
3.50
1.04
1.03
1.11
3.11
2.11
1.00
0.93
0.74
1.10
1.69
1.70
1.71
1.72
1.74
1.74
1.76
1.86
1.88
1.88
1.90
1.91
1.93
1.95
2.14
2.17
2.19
2.19
2.19
2.21
2.21
2.22
2.31
2.32
2.32
2.32
2.33
2.33
2.33
2.34
2.34
2.34
2.35
2.35
2.35
2.35
2.36
2.36
2.36
2.37
2.37
5.00
5.00
5.01
5.01
5.01
5.03
5.03
5.04
5.04
5.04
5.06
5.06
5.06
5.07
5.07
5.07
5.08
5.64
5.64
5.66
5.67
5.67
5.69
5.69
5.73
6.01
6.02
6.04
6.07
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 3.
OMe
HO
3
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S100
020406080100120140160180200220
ppm
20.36
21.79
33.58
41.07
44.07
116.96
118.74
133.51
145.57
200.31
Infrared spectrum (Thin Film, NaCl) of compound 3.
13C NMR (125 MHz, CDCl3) of compound 2p.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S101
01
23
45
67
89
10
ppm
3.00
1.00
0.96
1.16
3.34
2.30
1.10
1.21
0.99
2.11
2.15
1.17
1.80
1.81
1.81
1.82
1.96
1.96
1.97
2.25
2.26
2.28
2.43
2.44
2.44
2.45
2.45
2.45
2.45
2.46
2.46
2.46
2.46
2.46
2.47
2.47
2.47
2.47
2.48
2.48
2.49
5.07
5.07
5.07
5.08
5.09
5.09
5.09
5.09
5.11
5.11
5.11
5.11
5.73
5.75
5.77
5.79
6.33
6.34
6.34
6.89
6.91
6.91
6.91
6.92
7.02
7.03
7.03
7.03
7.04
7.04
7.04
7.04
7.25
7.25
7.25
7.26
7.26
7.26
7.27
7.28
7.28
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 4.
OMe
PhHN
4
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S102
020406080100120140160180200220
ppm
21.0
22.2
33.1
41.5
44.4
115.0
118.5
118.5
118.7
118.8
121.1
129.3
129.3
134.0
134.7
142.3
200.0
Infrared spectrum (Thin Film, NaCl) of compound 4.
13C NMR (125 MHz, CDCl3) of compound 4.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S103
01
23
45
67
89
10
ppm
3.00
1.02
1.01
1.01
1.01
2.02
2.00
1.02
1.00
1.00
1.00
1.00
1.00
1.29
2.04
2.05
2.05
2.07
2.07
2.08
2.22
2.23
2.23
2.24
2.25
2.26
2.36
2.37
2.39
2.40
2.55
2.57
2.58
2.59
3.01
3.02
3.03
3.04
3.04
3.05
3.05
3.07
5.10
5.11
5.11
5.12
5.12
5.13
5.13
5.14
5.14
5.14
5.14
5.84
5.87
5.88
5.90
7.14
7.14
7.15
7.16
7.16
7.17
7.17
7.36
7.36
7.38
7.38
7.38
7.39
7.39
7.48
7.48
7.48
7.49
7.50
7.50
7.65
7.65
7.66
7.67
7.67
7.67
9.75
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 5.
OMe
5
H N
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S104
020406080100120140160180200220
ppm
18.4
22.1
35.7
41.5
45.5
112.9
118.3
120.4
121.4
125.9
127.0
128.0
130.3
134.4
138.7
196.3
Infrared spectrum (Thin Film, NaCl) of compound 5.
13C NMR (125 MHz, CDCl3) of compound 5.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S105
01
23
45
67
89
10
ppm
2.92
3.02
0.97
0.99
1.00
0.99
2.01
3.01
2.03
2.04
1.00
2.11
2.01
1.17
1.41
1.42
1.44
1.96
1.96
1.97
1.98
1.99
1.99
2.00
2.10
2.12
2.12
2.13
2.13
2.14
2.15
2.25
2.27
2.28
2.28
2.28
2.29
2.30
2.30
2.40
2.40
2.41
2.41
2.42
2.42
2.43
2.44
3.10
3.11
3.11
3.11
3.12
3.12
3.13
3.14
3.85
4.42
4.44
4.45
4.46
5.06
5.06
5.06
5.07
5.09
5.09
5.09
5.09
5.10
5.10
5.11
5.11
5.11
5.11
5.73
5.75
5.75
5.76
5.77
5.79
6.93
6.95
7.35
7.37
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 6.
OMe
6
NN
MeO
2C
MeO
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S106
020406080100120140160180200220
ppm
14.3
14.6
18.6
21.6
34.9
40.8
46.7
55.7
60.5
61.3
113.8
118.8
127.1
132.8
132.9
133.6
135.2
140.0
160.0
162.3
192.7
Infrared spectrum (Thin Film, NaCl) of compound 6.
13C NMR (125 MHz, CDCl3) of compound 6.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S107
01
23
45
67
89
10
ppm
3.00
1.00
1.05
2.04
6.06
4.09
2.06
1.01
1.07
2.02
1.03
2.05
1.15
1.85
1.86
1.86
1.95
1.96
1.98
2.33
2.33
2.34
2.34
2.34
2.35
2.35
2.36
2.63
2.65
2.65
2.66
2.66
2.68
2.68
2.69
2.69
2.70
2.70
2.71
2.71
2.72
3.52
3.53
3.54
5.06
5.06
5.06
5.08
5.08
5.08
5.09
5.09
5.10
5.10
5.10
5.10
5.76
5.78
5.79
6.82
6.83
6.84
6.84
7.23
7.24
7.24
7.24
7.24
7.25
7.25
7.25
7.26
7.31
7.32
7.33
7.36
7.36
7.37
7.38
7.38
7.38
7.39
7.40
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 7.
OMe
NO
7Ph
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S108
020406080100120140160180200220
ppm
21.9
29.0
32.2
41.4
44.8
51.2
67.5
115.4
118.2
127.9
128.0
128.2
129.8
134.2
140.5
141.2
145.7
202.7
Infrared spectrum (Thin Film, NaCl) of compound 7.
13C NMR (125 MHz, CDCl3) of compound 7.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S109
01
23
45
67
89
10
ppm
1.97
0.99
1.00
4.88
4.88
5.57
5.57
5.60
5.60
5.60
5.61
5.61
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d SI
1 .
NCO
Cl
O
SI1
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S110
020406080100120140160180200220
ppm
69.7
108.9
118.5
118.5
132.9
143.5
Infrared spectrum (Thin Film, NaCl) of compound SI1.
13C NMR (125 MHz, CDCl3) of compound SI1.
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S111
01
23
45
67
89
10
ppm
2.97
2.00
2.00
1.81
1.81
1.82
4.73
4.74
5.08
5.08
5.09
5.09
5.09
5.09
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d SI
3.
NCO
Me
O
SI3
Supporting Information for Duquette, Cusumano, Lefoulon, Moore, and Stoltz
S112
020406080100120140160180200220
ppm
19.3
72.0
109.3
116.4
116.4
137.2
144.1
Infrared spectrum (Thin Film, NaCl) of compound SI3.
13C NMR (125 MHz, CDCl3) of compound SI3.