experimental procedures and characterization of the

2

Experimental Procedures and Characterization of the Prepared Compounds

The 1H-NMR and 13C-NMR spectra were recorded in CDCl3 (internal standard: 7.26

ppm, 1H; 77.36 ppm, 13C) at room temperature using Varian 300 or 400 MHz

spectrometers. Mass data (ESI) were obtained with a Bruker MicrOTOF spectrometer.

Palladium pincer-complex 4 was prepared according to the procedure published by

Yao and co-workers.[1] The aldehydes (2) and allylic alcohols (1) were purchased

from Aldrich or prepared according to literature procedures.[2] Diboronic acid 3 was

purchased from Boron Molecular Ltd and were used as received. For column

chromatography, Merck silica gel 60 (230-400 mesh) was used.

General Procedure. The corresponding allyl alcohol 1 (0.15 mmol) was dissolved in

the DMSO/MeOH mixture (0.3/0.3 ml) followed by addition of tetrahydroxydiboron

3 (0.18 mmol), pincer complex 4 (0.0075 mmol, 5 mol %), p-toluene sulfonic acid 5

(0.0075 mmol, 5 mol %) and aldehyde 2 (0.18 mmol). This reaction mixture was

stirred for the allotted temperatures and times listed in Tables 1-2 and thereafter

quenched with water and extracted with diethyl ether. After evaporation of the ether

phase, the product 6 was purified by silica gel column chromatography. The reactions

do not require use of inert atmosphere or application of carefully dried solvents.

1,2-Diphenyl-3-buten-1-ol (6a). This compound was prepared according to the

above general procedure from 1a and 2a. The NMR data obtained for 6a are identical

with the literature[3] values. 1H NMR (CDCl3): 7.18 (m, 8H), 7.06 (m, 2H), 6.26 (ddd,

8.3 Hz, 10.3 Hz, 17.1 Hz, 1H), 5.28 (d, 10.3 Hz, 1H), 5.23 (d, 17.1 Hz, 1H), 4.86 (dd,

2.7 Hz, 8.3 Hz, 1H), 3.56 (t, 8.3 Hz, 1H), 2.31 (d, 2.7 Hz, 1H) 13C NMR (CDCl3):

142.2, 141.0, 138.2, 128.7, 128.7, 128.3, 127.8, 127.0, 126.9, 118.8, 77.6, 59.6.

HRMS (ESI): calc for [C16H16O - OH]+: m/z, 207.1168, found: 207.1168.

1-(4-Bromophenyl)-2-phenyl-3-buten-1-ol (6b). This compound was prepared

according to the above general procedure from 1a and 2b. The diastereoselectivity of

6b is assigned on the basis of 1H-NMR data given in the literature[4] for analog stereo

defined homoallyl alcohols. 1H NMR (CDCl3): 7.32 (d, 8.4 Hz, 2H), 7.21 (m, 3H),

7.04 (d, 7.7 Hz, 2H), 7.00 (d, 8.4 Hz, 2H), 6.22 (ddd, 8.5 Hz, 10.1 Hz, 17.1 Hz, 1H),

5.29 (d, 10.1 Hz, 1H), 5.24 (d, 17.1 Hz, 1H), 4.79 (d, 8.5 Hz, 1H), 3.48 (t, 8.5 Hz,

Eur. J. Org. Chem. 2006 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006 · ISSN 1434–193X

SUPPORTING INFORMATION

Title: Highly Selective and Robust Palladium-Catalyzed Carbon–Carbon Coupling between Allyl Alcohols and Aldehydes via Transient Allylboronic Acids Author(s): Nicklas Selander, Sara Sebelius, Cesar Estay, Kálmán J. Szabó* Ref. No.: O200600530

3

1H), 2.37 (bs, 1H). 13C NMR (CDCl3): 141.1, 140.5, 137.8, 131.3, 128.8, 128.7,

128.6, 127.1, 121.6, 119.2, 76.9, 59.7. HRMS (ESI): calc for [C16H15BrO - OH]+: m/z,

285.0273, found: 285.0268.

1-(4-Cyanophenyl)-2-phenyl-3-buten-1-ol (6c). This compound was prepared

according to the above general procedure from 1a and 2c. The NMR data obtained for

6c are identical with the literature[5] values. 1H NMR (CDCl3): 7.48 (d, 8.1 Hz, 2H),

7.22 (m, 5H), 7.02 (d, 8.1 Hz, 2H), 6.22 (ddd, 8.5 Hz, 10.2 Hz, 17.1 Hz, 1H), 5.31 (d,

10.2 Hz, 1H), 5.25 (d, 17.1 Hz, 1H), 4.87 (d, 8.5 Hz, 1H), 3.45 (t, 8.5 Hz, 1H), 2.47

(bs, 1H). 13C NMR (CDCl3): 147.5, 139.9, 137.2, 132.0, 129.0, 128.5, 127.7, 127.4,

119.7, 119.2, 111.5, 76.9, 59.8. HRMS (ESI): calc for [C17H15NO + H]+: m/z,

250.1226, found: 250.1227.

1-(4-Nitrophenyl)-2-phenyl-3-buten-1-ol (6d). This compound was prepared

according to the above general procedure from 1a and 2d. The NMR data obtained for

6d are identical with the literature[6] values. 1H NMR (CDCl3): 8.07 (d, 8.8 Hz, 2H),

7.27 (d, 8.8 Hz, 2H), 7.21 (m, 3H), 7.04 (m, 2H), 6.23 (ddd, 8.5 Hz, 10.3 Hz, 17.1 Hz,

1H), 5.31 (d, 10.3 Hz, 1H), 5.20 (d, 17.1 Hz, 1H), 4.92 (d, 8.5 Hz, 1H), 3.47 (t, 8.5

Hz, 1H), 2.54 (bs, 1H) 13C NMR (CDCl3): 149.5, 147.5, 139.9, 137.1, 129.0, 128.5,

127.8, 127.5, 123.4, 119.8, 76.7, 59.8. HRMS (ESI): calc for [C16H15NO3 + H]+: m/z,

270.1125, found: 270.1124.

1-(4-Acetylphenyl)-2-phenyl-3-buten-1-ol (6e). This compound was prepared

according to the above general procedure from 1a and 2e. The diastereoselectivity of

6e is assigned on the basis of 1H-NMR data given in the literature[4] for analog stereo

defined homoallyl alcohols. 1H NMR (CDCl3): 7.79 (d, 8.4 Hz, 2H), 7.22 (d, 8.4 Hz,

2H), 7.19 (t, 6.6 Hz, 2H), 7.16 (t, 6.6 Hz, 1H), 7.05 (d, 6.6 Hz, 2H), 6.24 (ddd, 8.2 Hz,

10.2 Hz, 17.1 Hz, 1H), 5.28 (d, 10.2 Hz, 1H), 5.23 (d, 17.1 Hz, 1H), 4.90 (d, 8.2 Hz,

1H), 3.52 (t, 8.2 Hz, 1H), 2.54 (s, 3H), 2.50 (bs, 1H). 13C NMR (CDCl3): 198.2,

147.6, 140.4, 137.6, 136.5, 128.9, 128.6, 128.3, 127.2, 127.2, 119.3, 77.1, 59.6, 26.9.

HRMS (ESI): calc for [C18H18O2+H]+: m/z, 267.1380, found: 267.1387.

3-Phenyl-1-nonen-4-ol (6f). This compound was prepared according to the above

general procedure from 1a and 2f, except that 0.20 mmol of aldehyde 2f was used in a

4

0.2/0.2 ml DMSO/MeOH mixture. The NMR data obtained for 6f are identical with

the literature[3b] values. 1H NMR (CDCl3): 7.28 (m, 5H), 6.13 (ddd, 8.8 Hz, 10.2 Hz,

16.9 Hz, 1H), 5.24 (d, 10.2 Hz, 1H), 5.20 (d, 16.9 Hz, 1H), 3.80 (tt, 3.6 Hz, 7.1 Hz,

1H), 3.25 (dd, 7.1 Hz, 8.8 Hz, 1H), 1.79 (d, 3.6 Hz, 1H), 1.30 (m, 8H), 0.85 (t, 7.1 Hz,

3H). 13C NMR (CDCl3): 142.1, 138.7, 129.0, 128.3, 127.0, 118.2, 74.3, 57.8, 34.7,

32.1, 25.7, 22.9, 14.4. HRMS (ESI): calc for [C15H22O - OH]+: m/z, 201.1638, found:

201.1638.

2-Pentyl-1-phenyl-3-buten-1-ol (6g). This compound was prepared according to

the above general procedure from 1b and 2a, except that a 0.2/0.2 ml DMSO/MeOH

mixture was used. The NMR data obtained for 6g are identical with the literature[7]

values. 1H NMR (CDCl3): 7.30 (m, 5H), 5.66 (ddd, 8.1 Hz, 10.2 Hz, 17.2 Hz, 1H),

5.25 (d, 10.2 Hz, 1H), 5.18 (d, 17.2 Hz, 1H), 4.39 (d, 8.1 Hz, 1H), 2.29 (p, 8.1 Hz,

1H), 2.19 (bs, 1H), 1.18 (m, 8H), 0.82 (t, 7.0, 3H). 13C NMR (CDCl3): 142.9, 139.8,

128.6, 127.9, 127.3, 119.0, 77.0, 53.1, 32.0, 30.7, 27.2, 22.8, 14.3. HRMS (ESI): calc

for [C15H22O - OH]+: m/z, 201.1638, found: 201.1634.

3-Pentyl-1-nonen-4-ol (6h). This compound was prepared according to the above

general procedure from 1b and 2f, except that 0.20 mmol of aldehyde 2f was used in a

0.2/0.2 ml DMSO/MeOH mixture. The diastereoselectivity of 6h is assigned on the

basis of 1H-NMR data given in the literature[7] for analog stereo defined homoallyl

alcohols. 1H NMR (CDCl3): 5.63 (ddd, 9.3 Hz, 10.3 Hz, 17.1 Hz, 1H), 5.17 (d, 10.3

Hz, 1H), 5.08 (d, 17.1 Hz, 1H), 3.44 (m, 1H), 1.99 (tt, 4.7 Hz, 9.3 Hz, 1H), 1.37 (m,

17H), 0.88 (m, 6H). 13C NMR (CDCl3): 139.4, 118.0, 74.0, 50.7, 35.0, 32.3, 32.2,

31.1, 27.4, 25.8, 23.0, 22.9, 14.4, 14.4. HRMS (ESI): calc for [C14H28O]+: m/z,

212.2135, found: 212.2138.

2-[(Benzyloxy)methyl]-1-phenyl-3-buten-1-ol (6i). This compound was prepared

according to the above general procedure from 1c and 2a. The NMR data obtained for

6i are identical with the literature[8] values. 1H NMR (CDCl3): 7.34 (m, 10H), 5.89

(ddd, 8.4 Hz, 10.4 Hz, 17.2 Hz, 1H), 5.20 (d, 10.4 Hz, 1H), 5.11 (d, 17.2 Hz, 1H),

4.92 (dd, 3.8 Hz, 5.0 Hz, 1H), 4.51 (s, 2H), 3.57 (dd, 5.9 Hz, 9.2 Hz, 1H), 3.52 (dd,

5.0 Hz, 9.2 Hz, 1H), 3.00 (d, 3.8 Hz, 1H), 2.71 (ddt, 5.0 Hz, 5.9 Hz, 8.4 Hz, 1H). 13C

NMR (CDCl3): 142.6, 138.2, 135.6, 128.7, 128.3, 128.0, 128.0, 127.6, 126.7, 118.8,

5

74.9, 73.7, 71.9, 51.7. HRMS (ESI): calc for [C18H20O2 + H]+: m/z, 269.1536, found:

259.1535.

1-Phenyl-2-vinyl-3-buten-1-ol (6j). This compound was prepared according to the

above general procedure from 1d and 2a. The NMR data obtained for 6j are identical

with the literature[9] values. 1H NMR (CDCl3): 7.31 (m, 5H), 5.86 (ddd, 7.2 Hz, 10.4

Hz, 17.1 Hz, 1H), 5.69 (ddd, 7.2 Hz, 10.6 Hz, 17.3 Hz, 1H), 5.24 (d, 10.4 Hz, 1H),

5.18 (d, 17.1 Hz, 1H), 5.05 (d, 10.6 Hz, 1H), 5.02 (d, 17.3 Hz, 1H), 4.60 (dd, 3.1 Hz,

7.2 Hz, 1H), 3.11 (q, 7.2 Hz, 1H), 2.19 (d, 3.1 Hz, 1H). 13C NMR (CDCl3): 142.1,

137.1, 137.1, 128.5, 128.0, 127.2, 118.7, 117.4, 76.5, 56.5. HRMS (ESI): calc for

[C12H14O - OH]+: m/z, 157.1012, found: 157.1015.

Ethyl 2-(2-hydroxy-2-phenylethyl)acrylate (6k). This compound was prepared

according to the above general procedure from 1e and 2a. The NMR data obtained for

6k are identical with the literature[10] values. 1H NMR (CDCl3): 7.37 (d, 7.8 Hz, 2H),

7.34 (t, 7.8 Hz, 2H), 7.26 (t, 7.8 Hz, 1H), 6.24 (s, 1H), 5.60 (s, 1H), 4.89 (dt, 3.8 Hz,

8.6 Hz, 1H), 4.23 (q, 7.2 Hz, 2H), 2.80 (dd, 3.8 Hz, 14.0 Hz, 1H), 2.69 (d, 3.8 Hz,

1H), 2.67 (dd, 8.6 Hz, 14.0 Hz, 1H), 1.32 (t, 7.2 Hz, 3H). 13C NMR (CDCl3): 168.1,

144.3, 137.5, 128.7, 128.5, 127.8, 126.1, 73.5, 61.4, 42.9, 14.5. HRMS (ESI): calc for

[C13H16O3 + H]+: m/z, 221.1172, found: 221.1170.

4-Phenyl-2-methylenebutyrolactone (6l). This compound was prepared according

to the above general procedure from 1e and 2a, except that 50 mol% p-

toluenesulfonic acid was used. The NMR data obtained for 6l are identical with the

literature[11] values. 1H NMR (CDCl3): 7.36 (m, 5H), 6.31 (t, 2.6 Hz, 1H), 5.69 (t, 2.6

Hz, 1H), 5.53 (dd, 6.7 Hz, 7.8 Hz, 1H), 3.41 (ddt, 2.6 Hz, 7.8 Hz, 17.1 Hz, 1H), 2.92

(ddt, 2.6 Hz, 6.7 Hz, 17.1 Hz, 1H). 13C NMR (CDCl3): 170.5, 140.2, 134.6, 129.2,

128.9, 125.7, 122.8, 78.3, 36.6. HRMS (ESI): calc for [C11H10O2 + H]+: m/z,

175.0754, found: 175.0755.

2-Cyclohexenyl(phenyl)methanol (6m). This compound was prepared according

to the above general procedure from 1f and 2a. The NMR data obtained for 6m are

identical with the literature[9] values. 1H NMR (CDCl3): 7.35 (d, 4.4 Hz, 4H), 7.28

(m, 1H), 5.82 (dt, 4.9 Hz, 10.2 Hz, 1H), 5.39 (dd, 5.1 Hz, 10.2 Hz, 1H), 4.59 (dd, 2.8

6

Hz, 6.5 Hz, 1H), 2.51 (ddt, 5.1 Hz, 6.5 Hz, 17.4 Hz, 1H), 1.99 (m, 2H), 1.87 (d, 2.8

Hz, 1H), 1.74 (m, 2H), 1.53 (m, 2H). 13C NMR (CDCl3): 143.2, 130.8, 128.6, 128.4,

127.8, 126.9, 77.7, 43.4, 25.6, 24.2, 21.5. HRMS (ESI): calc for [C13H16O + H]+: m/z,

189.1274, found: 189.1273.

Methyl 5-[hydroxy(phenyl)methyl]-3-cyclohexene-1-carboxylate (6n). This

compound was prepared according to the above general procedure from 1g and 2a,

except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml

DMSO/MeOH mixture. The diastereoselectivity of 6n is assigned on the basis of 1H-

NMR data given in the literature[9,12] for analog stereo defined compounds. 1H NMR

(CDCl3): 7.32 (m, 5H), 5.79 (m, 1H), 5.30 (m, 1H), 4.56 (d, 7.1 Hz, 1H), 3.68 (s, 3H),

2.76 (dtd, 3.7 Hz, 7.1 Hz, 10.2 Hz, 1H), 2.57, (m, 1H), 2.26 (m, 2H), 2.14 (dt, 3.7 Hz,

13.5 Hz, 1H), 2.02 (bs, 1H), 1.81 (ddd, 6.0 Hz, 10.2 Hz, 13.5 Hz, 1H). 13C NMR

(CDCl3): 176.4, 143.0, 128.7, 128.3, 128.0, 127.7, 126.8, 77.0, 52.0, 41.3, 36.5, 27.6,

26.1. HRMS (ESI): calc for [C15H18O3 - OH]+: m/z, 229.1223, found: 229.1223.

Methyl 5-[(4-bromophenyl)(hydroxy)methyl]-3-cyclohexene-1-carboxylate

(6o). This compound was prepared according to the above general procedure from 1g

and 2b, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml

DMSO/MeOH mixture. The diastereoselectivity of 6o is assigned on the basis of 1H-


(CDCl3): 7.47 (d, 8.4 Hz, 2H), 7.21 (d, 8.4 Hz, 2H), 5.80 (m, 1H), 5.30 (m, 1H), 4.54

(d, 7.2 Hz, 1H), 3.66 (s, 3H), 2.73 (dtd, 3.8 Hz, 7.0 Hz, 10.2 Hz, 1H), 2.52 (m, 1H),

2.26 (m, 2H), 2.13 (bs, 1H), 2.06 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.76 (ddd, 6.1 Hz, 10.2

Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 176.3, 141.9, 131.7, 128.8, 128.5, 127.3, 121.7,

76.2, 52.1, 41.3, 36.5, 27.5, 25.8. HRMS (ESI): calc for [C15H17BrO3 - OH]+: m/z,

307.0328, found: 307.0323.

Methyl 5-[(4-cyanophenyl)(hydroxy)methyl]-3-cyclohexene-1-carboxylate (6p).

This compound was prepared according to the above general procedure from 1g and

2c, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml

DMSO/MeOH mixture. The diastereoselectivity of 6p is assigned on the basis of 1H-



7

(dd, 2.5 Hz, 6.5 Hz, 1H), 3.66 (s, 3H), 2.75 (dtd, 3.8 Hz, 6.8 Hz, 9.8 Hz, 1H), 2.56 (m,

1H), 2.27 (m, 2H), 2.23 (d, 2.5 Hz, 1H), 1.99 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.72 (ddd, 6.0

Hz, 9.8 Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 176.1, 148.2, 132.5, 129.6, 127.5,

126.9, 119.1, 111.6, 76.1, 52.1, 41.2, 36.5, 27.5, 25.4. HRMS (ESI): calc for

[C16H17NO3+H]+: m/z, 272.1281, found: 272.1286.

Methyl 5-[hydroxy(4-nitrophenyl)methyl]-3-cyclohexene-1-carboxylate (6q).


2d, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml

DMSO/MeOH mixture. The diastereoselectivity of 6q is assigned on the basis of 1H-



(d, 6.5 Hz, 1H), 3.65 (s, 3H), 2.75 (dtd, 3.8 Hz, 7.0 Hz, 10.0 Hz, 1H), 2.58 (m, 1H),

2.43 (bs, 1H), 2.27 (m, 2H), 1.99 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.71 (ddd, 6.2 Hz, 10.0

Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 176.1, 150.3, 147.6, 129.6, 127.5, 126.8, 123.8,

75.9, 52.1, 41.3, 36.5, 27.4, 25.4. HRMS (ESI): calc for [C15H17NO5+H]+: m/z,

292.1179, found: 292.1181.

Methyl 5-[(4-acetylphenyl)(hydroxy)methyl]-3-cyclohexene-1-carboxylate (6r).


2e, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml

DMSO/MeOH mixture. The diastereoselectivity of 6r is assigned on the basis of 1H-



(d, 6.6 Hz, 1H), 3.66 (s, 3H), 2.76 (dtd, 3.8 Hz, 6.8 Hz, 10.0 Hz, 1H), 2.59 (s, 3H),

2.59 (m, 1H), 2.27 (m, 3H), 2.05 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.75 (ddd, 6.1 Hz, 10.0

Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 198.2, 176.2, 148.3, 136.7, 129.0, 128.7, 127.2,

126.9, 76.4, 52.1, 41.3, 36.5, 27.5, 26.9, 25.7. HRMS (ESI): calc for [C17H20O4+H]+:

m/z, 289.1434, found: 289.1430.

Methyl 5-(1-hydroxyhexyl)-3-cyclohexene-1-carboxylate (6s). This compound

was prepared according to the above general procedure from 1g and 2f, except that

0.20 mmol of aldehyde 2f and 0.30 mmol of tetrahydroxydiboron were used in a

0.2/0.2 ml DMSO/MeOH mixture. The diastereoselectivity of 6s is assigned on the

8

basis of 1H-NMR data given in the literature[9,12] for analog stereo defined

compounds. 1H NMR (CDCl3): 5.85 (m, 1H), 5.60 (m, 1H), 3.68 (s, 3H), 3.56 (dt, 5.1

Hz, 6.7 Hz, 1H), 2.79 (dtd, 3.7 Hz, 6.1 Hz, 9.3 Hz, 1H), 2.26 (m, 3H), 2.02 (dt, 3.7

Hz, 13.5 Hz, 1H), 1.82 (ddd, 6.0 Hz, 9.3 Hz, 13.5 Hz, 1H), 1.41 (m, 9H), 0.89 (t, 6.6

Hz). 13C NMR (CDCl3): 176.4, 128.4, 128.4, 74.3, 52.0, 39.5, 36.8, 34.5, 32.2, 27.5,

25.9, 25.1, 23.0, 14.4. HRMS (ESI): calc for [C14H24O3+H]+: m/z, 241.1798, found:

241.1800.

Methyl 5-[hydroxy(3-nitrophenyl)methyl]-3-cyclohexene-1-carboxylate (6t).


2g, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml

DMSO/MeOH mixture. The diastereoselectivity of 6t is assigned on the basis of 1H-


(CDCl3): 8.21 (s, 1H), 8.13 (d, 8.0 Hz, 1H), 7.68 (d, 8.0 Hz, 1H), 7.52 (t, 8.0 Hz, 1H),

5.87 (m, 1H), 5.34 (m, 1H), 4.74 (dd, 6.6 Hz, 2.9 Hz, 1H), 3.66 (s, 3H), 2.76 (dtd, 3.8

Hz, 6.7 Hz, 9.7 Hz, 1H), 2.60 (m, 1H), 2.34 (d, 2.9 Hz, 1H), 2.28 (m, 2H), 2.02 (dt,

3.8 Hz, 13.5 Hz, 1H), 1.75 (ddd, 6.0 Hz, 9.7 Hz, 13.5 Hz, 1H). 13C NMR (CDCl3):

176.1, 148.6, 145.0, 132.9, 129.6, 129.6, 126.8, 122.9, 121.8, 75.8, 52.1, 41.3, 36.5,

27.5, 25.5. HRMS (ESI): calc for [C15H17NO5+H]+: m/z, 292.1179, found: 292.1171.

Methyl 5-[1-hydroxymethyl]-3-cyclohexene-1-carboxylate (6u). This compound

was prepared according to the above general procedure from 1g and 2h, except that

0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml DMSO/MeOH mixture.

The diastereoselectivity of 6u is assigned on the basis of 1H-NMR data given in the

literature[9,12] for analog stereo defined compounds. 1H NMR (CDCl3): 5.82 (m, 1H),

5.62 (m, 1H), 3.68 (s, 3H), 3.56 (m, 2H), 2.71 (dtd, 4.3 Hz, 7.0 Hz, 9.9 Hz, 1H), 2.40

(m, 1H), 2.27 (m, 2H), 1.92 (m, 2H), 1.63 (bs, 1H), 13C NMR (CDCl3): 176.4, 128.1,

127.3, 66.3, 52.1, 36.8, 36.5, 27.6, 27.3. HRMS (ESI): calc for [C9H14O3 + H]+: m/z,

171.1016, found: 171.1017.

Methyl 5-[1-hydroxyethyl]-3-cyclohexene-1-carboxylate (6v). This compound

was prepared according to the above general procedure from 1g and 2i, except that

0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml DMSO/MeOH mixture.

The diastereoselectivity of 6u is assigned on the basis of 1H-NMR data given in the

9

literature[9,12] for analog stereo defined compounds. 1H NMR (CDCl3): 5.82 (m, 1H),

5.60 (m, 1H), 3.72 (p, 6.2 Hz, 1H), 3.67 (s, 3H), 2.75 (dtd, 3.9 Hz, 6.8 Hz, 9.7 Hz,

1H), 2.26 (m, 2H), 2.16 (m, 1H), 2.02 (dt, 3.9 Hz, 13.5 Hz, 1H), 1.90 (bs, 1H), 1.83

(ddd, 6.0 Hz, 9.7 Hz, 13.5 Hz, 1H), 1.22 (d, 6.2 Hz, 3H). 13C NMR (CDCl3): 176.4,

128.2, 128.0, 70.3, 52.0, 41.2, 36.7, 27.5, 25.5, 21.0. HRMS (ESI): calc for [C10H16O3

+ H]+: m/z, 185.1172, found: 185.1170.

10

OH

Ph 6a

11

OH

Ph 6a

12

OH

PhBr

6b

13

OH

PhBr

6b

14

OH

PhC

N6c

15

OH

PhC

N6c

16

OH

PhN

O2

6d

17

OH

PhN

O2

6d

18

OH

PhO

6e

19

OH

PhO

6e

20

OH

Ph6f

21

OH

Ph6f

22

OH

C5H

11 6g

23

OH

C5H

11 6g

24

OH

C5H

11

6h

25

OH

C5H

11

6h

26

OH

BnO

6i

27

OH

BnO

6i

28

OH

6j

29

OH

6j

30

OH

CO

OEt

6k

31

OH

CO

OEt

6k

32

OO

6l

33

OO

6l

34

OH

H 6m

35

OH

H 6m

36

OH

CO

OM

e

6nH

37

OH

CO

OM

e

6nH

38

OH

CO

OM

eBr

6o

H

39

OH

CO

OM

eBr

6o

H

40

OH

CO

OM

eC

N

6p

H

41

OH

CO

OM

eC

N

6p

H

42

OH

CO

OM

eN

O2

6q

H

43

OH

CO

OM

eN

O2

6q

H

44

OH

CO

OM

e 6r

O

H

45

OH

CO

OM

e 6r

O

H

46

OH

CO

OM

e 6s

H

47

OH

CO

OM

e 6s

H

48

6tOH

CO

OM

e

NO

2H

49

6tOH

CO

OM

e

NO

2H

50

HO

CO

OM

e

6u

51

HO

CO

OM

e

6u

52

OH

CO

OM

e

H 6v

53

OH

CO

OM

e

H 6v

54

References

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2577. (b) D. Basavaiah, P. D. Rao, Tetrahedron: Asymmetry 1995, 6, 789.

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[5] J. M. Coxon, S. J. van Eyk, P. J. Steel, Tetrahedron, 1989, 45, 1029.

[6] O. A. Wallner, K. J. Szabó, J. Org. Chem. 2003, 68, 2934.

[7] K. Fujita, H. Yorimitsu, H. Shinokubo, S. Matsubara, K. Oshima, J. Am.

Chem. Soc. 2001, 123, 12115.

[8] M. Bandini, P. G. Cozzi, S. Licciulli, A. Umani-Ronchi, Synthesis 2004,

409.

[9] S. Kobayashi, K. Nishio, J. Org. Chem. 1994, 59, 6620.

[10] H. Nagano, S. Toi, M. Matsuda, T. Hirasawa, S. Hirasawa, T. Yajima, J.

Chem. Soc. Perkin Trans.2, 2002, 22, 2525.

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[12] V. J. Olsson, S. Sebelius, N. Selander, K. J. Szabó, J. Am. Chem. Soc., 2006,

128, 4588.

experimental procedures and characterization of the

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