supporting information for - rsc.org · supporting information for alkali metal catalyzed...
TRANSCRIPT
![Page 1: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/1.jpg)
Supporting Information for
Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond
A. Harinath,a Srinivas Anga,a and Tarun K. Panda*a
Table of Contents
S1.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [{(CH3)2CH}2NBpin] (E)
S2.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [{(CH3)2CH}2NBpin] (E)
S3.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [{(CH3)2CH}2NBpin] (E)
S4.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (G)
S5.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (G)
S6.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (G)
S7.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (I)
S8.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (I)
S9.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (I)
S10.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C8H10ON(H)Bpin] (J)
S11.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C8H10ON(H)Bpin] (J)
S12.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C8H10ON(H)Bpin] (J)
S13.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C6H4FN(H)Bpin] (K)
S14.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C6H4FN(H)Bpin] (K)
S15.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C6H4FN(H)Bpin] (K)
S16.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C6H4NO2N(H)Bpin] (L)
S17.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C6H4NO2N(H)Bpin] (L)
S18.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C6H4NO2N(H)Bpin] (L)
S19.1H NMR spectrum (400 MHz, 25°C, CDCl3) [C5H4N2(H)Bpin] (M)
S20.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C5H4N2(H)Bpin] (M)
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
![Page 2: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/2.jpg)
S21.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C5H4N2(H)Bpin] (M)
S22.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C8H6NBpin] (N)
S23.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C8H6NBpin] (N)
S24.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C8H6NBpin] (N)
S25.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C8H8NBpin] (O)
S26.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C8H8NBpin] (O)
S27.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C8H8NBpin] (O)
S28.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C3H5N(H)Bpin] (P)
S29.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C3H5N(H)Bpin] (P)
S30.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [C3H5N(H)Bpin] (P)
S31.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [(CH3CH2)2NBR2] (Q)
S32.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [(CH3CH2)2NBR2] (Q)
S33.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [(CH2)4NBR2] (R)
S34.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [(CH2)4NBR2] (R)
S35.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C6H4FN(H)BR2] (U)
S36.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C6H4FN(H)BR2] (U)
![Page 3: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/3.jpg)
A1. Experimental section
General: All manipulations of air-sensitive materials were performed with the rigorous
exclusion of oxygen and moisture in flame dried Schlenk-type glassware, either on a dual
manifold Schlenk line interfaced with a high vacuum (10−4 torr) line, or in an argon-filled M.
Braun glovebox. The 1H NMR (400 MHz), 11B{1H} (128 MHz), 13C{1H} (100 MHz), spectra
were recorded on a BRUKER AVANCE III-400 spectrometer. All catalytic substrates amines
and boranes were purchased from either Sigma Aldrich or Alfa Aesar. Amines were distilled
over CaH2 prior to use. LiN(SiMe3)2, NaN(SiMe3)2 and KN(SiMe3)2 were purchased from Sigma
Aldrich and used as received. CDCl3 was purchased from Sigma Aldrich.
A2. Typical procedure for CDC reactions: Catalyzed cross-dehydrocoupling (CDC) reactions
were carried out by using the following standard protocol. In the glove-box, the pre-catalyst
chosen (0.05 mmol) was loaded into a Schleck tube and subsequently the amine (n × 0.05 mmol,
n equi) followed by borane (n × 0.05 mmol, n equi) were added to the Schleck tube. The reaction
![Page 4: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/4.jpg)
was stirred in an oil bath at desired temperature (25°C). After the required amount of time, the
reaction was quenched by adding CDCl3 to the reaction mixture. Substrate conversion was
monitored by the 1H NMR spectrum of the reaction mixture, comparing integrations
characteristic of the substrates and products. Novel compounds characterized here after.
Product – E
NBO
O
C6H14NBpin:- 1H NMR (400 MHz, CDCl3) δ 3.34 (m, 2H, CH), 1.18 (s, 12H), 1.10 (s, 12H)
ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 80.9 (O attached C), 44.5 (CH), 24.5 (CH3-C), 23.2
(CH3-C) ppm. 11B{1H} NMR (128 MHz, CDCl3) δ 23.8 ppm.
Product – G
OB
O HN
Ph
C7H7NBpin:- 1H NMR (400 MHz, CDCl3) δ 7.23-7.17 (m, 3H, Ar-H), 7.15 - 7.10 ( m, 2H, Ar-
H) 4.01 (d, 2H, J =7.7 Hz, CH2), 1.15 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 142.8
(Ar-C), 128.3 (Ar-C), 126.7 (Ar-C) 82.1 (O attached C), 45.2 (CH3), 24.6 (CH3-C) ppm. 11B{1H}
NMR (128 MHz, CDCl3) δ 24.8 ppm.
Product – I
OB
O HN Me
![Page 5: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/5.jpg)
C7H7N(H)Bpin:- 1H NMR (400 MHz, CDCl3) δ 7.01-6.95 (m, 4H, Ar-H), 4.53 (br, 1H, NH),
2.25 (s, 3H), 1.29 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 140.6 (N attached Ar-C),
129.4 (Ar-C), 117.5 (Ar-C), 121.3 (Ar-C), 119.3 (Ar-C), 118.9 (Ar-C), 83.6 (O attached C), 24.6
(CH3-C), 20.5 (CH3-C) ppm.11B{1H} NMR (128 MHz, CDCl3) δ 23.9 ppm.
Product – J
OB
O HN OMe
C8H9ON(H)Bpin:- 1H NMR (400 MHz, CDCl3) δ 7.41 (d, 1H, J = 8.4 Hz, Ar-H), 6.71-6.67
(m, 2H, Ar-H), 4.37 (br, 1H, NH), 3.75 (s, 3H), 2.18 (s, 3H), 1.31 (s, 12H) ppm. 13C{1H} NMR
(100 MHz, CDCl3) δ 153.6 (N attached Ar-C), 129.4 (Ar-C), 117.5 (Ar- C), 121.3 (Ar- C), 119.3
(Ar- C), 118.9 (Ar- C), 82.6 (O attached C), 55.5 (O attached C), 24.6 (CH3-C), 18.1 (CH3- C)
ppm. 11B{1H} NMR (128 MHz, CDCl3) δ 24.1 ppm.
Product - K
OB
O HN
F
C6H4FN(H)Bpin:- 1H NMR (400 MHz, CDCl3) δ 7.61-7.57 (d, 1H, Ar-H), 7.02 - 6.95 (m, 2H,
Ar-H), 6.80-6.74 (m, 1H, Ar-H), 4.97 (br, 1H, NH), 1.32 (s, 12H) ppm. 13C {1H} NMR (100
MHz, CDCl3) δ 153.4 (F attached Ar-C), 151.0 (N attached Ar-C), 131.6 (Ar-C), 124.3 (Ar-C),
119.1 (Ar-C), 114.5 (Ar-C), 83.0 (O attached C), 24.6 (CH3-C). 11B{1H} NMR (128 MHz,
CDCl3) δ 24.04 ppm.
Product - L
OB
O HN
O2N
C6H4NO2N(H)Bpin:- 1H NMR (400 MHz, CDCl3) δ 8.05 (br, 1H, NH), 7.93-7.87 (m, 2H, Ar-
H), 7.72 (d, 1H, J = 8.4), 7.14 (t, 1H, J = 7.8 Hz, Ar-H), 1.16 (s, 12H, CH3 – H) ppm . 13C{1H}
![Page 6: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/6.jpg)
NMR (100 MHz, CDCl3) δ 145.0 (N attached Ar-C), 135.6 (Ar-C), 135.2 (Ar-C), 121.3 (Ar-C),
119.3 (Ar-C), 118.9 (Ar-C), 83.6 (O attached C), 24.5 (CH3-C) ppm. 11B{1H} NMR (128 MHz,
CDCl3) δ 24.32 ppm.
Product – M
OB
O HN
N
C5H4N2(H)Bpin:- 1H NMR (400 MHz, CDCl3) δ 8.13 (d, 1H, J = 3.9 Hz Ar-H), 7.51 - 7.47 (m,
1H, Ar-H ), 7.41-7.33 (m, 1H, Ar-H), 6.77-6.72 (m, 1H, Ar-H ), 5.76 (br, 1H, NH), 1.29 (s,
12H) ppm.13C{1H} NMR (100 MHz, CDCl3) δ 156.3 (N attached Ar-C), 147.8 (N attached Ar-
C), 137.2 (Ar-C), 111.5 (Ar-C), 108.5 (Ar-C), 83.1 (O attached C), 24.6 (CH3-C) ppm. 11B{1H}
NMR (128 MHz, CDCl3 ) δ 23.99 ppm.
Product – N
OB
ON
C8H6NBpin:- 1H NMR (400 MHz, CDCl3) δ 7.78 (d, 1H, J = 7.9, C=CH ), 7.41 (d, 1H, J = 7.3
Hz), 7.20 (d, 1H, J = 3.2 Hz), 7.06-7.04 (m, 1H, Ar-H ), 7.00 - 6.97 (m, 1H, Ar-H ), 6.41 (d, 1H,
J = 3.3 Hz, C=CH), 1.21 (s, 12H) ppm. 13C {1H} NMR (100 MHz, CDCl3) δ 135.8 (N attached
Ar-C), 135.0 (Ar-C), 134.8 (Ar-C), 133.7 (Ar-C), 131.6 (Ar-C), 130.3 (Ar-C), 130.4 (Ar-C),
127.9 (Ar-C), 127.8 (Ar-C) ppm. 11B{1H} NMR (128 MHz, CDCl3) δ 24.5 ppm.
Product - O
OB
ON
![Page 7: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/7.jpg)
C9H8N(H)Bpin:- 1H NMR (400 MHz, CDCl3) δ 7.99 (d, 1H, J = 8.1 Hz, C = CH), 7.65 (d, 1H, J
= 7.8 Hz), 7.58 (d, 1H, J = 7.5 Hz), 7.38 (d, 1H, J = 7.9 Hz) 7.31 - 7.19 (m, 6H, Ar-H), 6.99 (d,
1H, Ar-H), 2.36 (s, 3H), 1.40 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 139.6 (N
attached Ar-C), 136.2 (Ar-C), 131.9 (Ar-C), 126.0 (Ar-C), 122.6 (Ar-C), 120.8 (Ar-C), 118.5
(Ar-C), 114.6 (Ar-C), 110.9 (Ar-C), 84.1 (O attached C), 24.7 (CH3-C), 9.71 (CH3-C) ppm. 11B{1H} NMR (128 MHz, CDCl3) δ 24.35 ppm.
Product – P
OB
ONH
C3H5N(H)Bpin:- 1H NMR (400 MHz, CDCl3) δ 5.86 - 5.79 (m, 1H, CH) 5.09 - 5.04 (d, J = 1.7,
17.1 Hz, 1H, CH), 4.95 - 4.92 (m, 1H, CH), 3.45 (m, 1H), 3.45 (m, 2H, CH2), 2.25 (br, 1H, NH),
1.16 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 81.9 (O attached C), 43.4 (CH), 24.5
(CH3 - C), 24.4 ( CH3-C ) ppm. 11B{1H} NMR (128 MHz, CDCl3) δ 24.35 ppm.
Product – Q
N B
C4H10NBR2: 1H NMR (400 MHz, CDCl3) δ 3.05 - 3.00 (q, J = 7.1, 7.0 Hz, 4H, CH2 ), 1.83 -
1.57 (m, 5H, CH2), 1.32 - 1.25 (m, 2H, CH), 0.99 (t, 6H, J = 7.0 Hz, CH3) ppm. 13C{1H} NMR
(100 MHz, CDCl3) 40.4, 30.9, 21.0, 14.5 ppm. 11B{1H} NMR (128 MHz, CDCl3): δ 47.7 ppm.
Product – R
N B
![Page 8: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/8.jpg)
C4H8NBR2: 1H NMR (400 MHz, CDCl3) δ 3.29 - 3.26 (m, 4H, CH2), 1.89 - 1.63 (m, 14H,
CH,CH2), 1.37 - 1.36 (m, 4H, CH2), 3.45 (m, 1H) ppm. 13C{1H} NMR (100 MHz, CDCl3) 44.6,
30.5, 23.7, 21.2 ppm. 11B{1H} NMR (128 MHz, CDCl3): δ 48.4 ppm.
Product – U
HN B
F
C6H4FN(H)BR2: 1H NMR (400 MHz, CDCl3) δ 7.14-7.08 (m, 1H, Ar-H), 7.01 - 6.87 (m, 2H,
Ar-H), 6.70-6.57 (m, 1H, Ar-H), 5.97 (br, 1H, NH), 1.90 -1.03 (m, 14H) ppm. 11B{1H} NMR
(128 MHz, CDCl3): δ 52.8 ppm.
![Page 9: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/9.jpg)
![Page 10: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/10.jpg)
9 8 7 6 5 4 3 2 1
Chemical Shift (ppm)
12.3012.692.09
7.26 3.34 3.33 1.18 1.10 0.07
S1.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [(CH3)2CHNBpin] (E)
S2.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [(CH3)2CHNBpin] (E)
NBO
O
NBO
O
100 80 60 40 20 0 -20 -40 -60 -80 -100Chemical Shift (ppm)
23.90
![Page 11: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/11.jpg)
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5Chemical Shift (ppm)
80.91 77.06 44.53 23.21
S3.13C NMR spectrum (100 MHz, 25°C, CDCl3) of [(CH3)2CHNBpin] (E)
NBO
O
![Page 12: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/12.jpg)
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)
4.3712.230.781.011.012.068.35
8.23 7.17 7.14 4.69 4.00 3.77 2.63 2.44 1.13 1.06
S4.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (G)
NHBO
O
![Page 13: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/13.jpg)
40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
24.80
S5.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C7H7N(H)Bpin] (G)
NHBO
O
![Page 14: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/14.jpg)
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)
142.96 128.33 126.80 82.07 80.70 45.26 24.62
S6.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C7H7N(H)Bpin] (G)
NHBO
O
![Page 15: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/15.jpg)
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
0.4014.100.683.330.933.99
6.98 2.25 1.29 1.27
S7.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C7H7N(H)Bpin] (I)
NH
BO
O
![Page 16: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/16.jpg)
45 40 35 30 25 20 15 10 5Chemical Shift (ppm)
24.21
S8.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C7H7N(H)Bpin] (I)
NH
BO
O
![Page 17: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/17.jpg)
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)
140.67 129.49 117.57 77.33 76.70 24.64 20.55
S9.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C7H7N(H)Bpin] (I)
NH
BO
O
![Page 18: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/18.jpg)
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
0.6812.223.283.150.912.071.00
7.31 6.59 4.28 3.66 2.09 1.23 1.19 0.00
S10.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C8H10ON(H)Bpin](J)
NH
BO
OOMe
![Page 19: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/19.jpg)
55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
24.34
S11.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C8H10ON(H)Bpin](J)
NH
BO
OOMe
![Page 20: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/20.jpg)
220 200 180 160 140 120 100 80 60 40 20 0 -20Chemical Shift (ppm)
153.60 134.85 112.00 82.66 55.52 24.65 18.10
S12.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C8H10ON(H)Bpin] (J)
NH
BO
OOMe
![Page 21: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/21.jpg)
Fig-S4
9 8 7 6 5 4 3 2 1Chemical Shift (ppm)
11.520.831.021.990.94
7.26 7.00 4.97 1.32 0.07
S13.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C6H4FN(H)Bpin] (K)
NH
F
BO
O
![Page 22: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/22.jpg)
Fig-S5
45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
24.04
S14.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C6H4FN(H)Bpin] (K)
NH
F
BO
O
![Page 23: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/23.jpg)
220 200 180 160 140 120 100 80 60 40 20 0 -20Chemical Shift (ppm)
153.40 124.38 119.11 77.24 76.72 24.65
S15.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C6H4FN(H)Bpin] (K)
NH
F
BO
O
![Page 24: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/24.jpg)
9 8 7 6 5 4 3 2 1Chemical Shift (ppm)
9.0315.711.950.122.111.152.401.261.211.142.291.02
7.72 7.28 6.69 6.68 6.13 1.16 1.06
S16.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C6H4NO2N(H)Bpin] (L)
NHO2N
BO
O
![Page 25: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/25.jpg)
55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
24.32 21.10
S17.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C6H4NO2N(H)Bpin] (L)
NHO2N
BO
O
![Page 26: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/26.jpg)
220 200 180 160 140 120 100 80 60 40 20 0 -20Chemical Shift (ppm)
135.52 119.35 116.61 83.60 77.21 24.59 24.49 3.39
S18.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C6H4NO2N(H)Bpin] (L)
NHO2N
BO
O
![Page 27: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/27.jpg)
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)
0.8913.210.300.990.200.271.091.011.030.98
8.13 7.50 7.48 6.74 6.72 5.76 4.51 1.29 1.16 0.15
S19.1H NMR spectrum (400 MHz, 25°C, CDCl3) [C5H4N2(H)Bpin] (M)
OB
O HN
N
![Page 28: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/28.jpg)
60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
24.09
S20.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C5H4N2(H)Bpin] (M)
OB
O HN
N
![Page 29: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/29.jpg)
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)
147.83 137.72 111.53 108.58 76.74 24.62 3.39
S21.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C5H4N2(H)Bpin] (M)
OB
O HN
N
![Page 30: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/30.jpg)
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.5113.240.982.391.021.001.01
7.78 7.21 7.20 6.42 6.41 1.22 1.12 0.00
S22.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C8H6NBpin] (N)
NBO
O
![Page 31: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/31.jpg)
45 40 35 30 25 20 15 10 5Chemical Shift (ppm)
24.50
S23.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C8H6NBpin] (N)
NBO
O
![Page 32: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/32.jpg)
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)
127.97 127.84 77.20 76.89 59.06 18.50 18.34
S24.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C8H6NBpin] (N)
NBO
O
![Page 33: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/33.jpg)
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)
8.8916.383.572.980.914.670.831.060.880.531.07
7.98 7.26 7.22 2.36 2.35 1.45 1.30 0.25
S25.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C8H8NBpin] (O)
NBO
O
![Page 34: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/34.jpg)
38 36 34 32 30 28 26 24 22 20 18 16 14 12 10 8 6 4Chemical Shift (ppm)
28.26 24.35
S26.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C8H8NBpin] (O)
NBO
O
![Page 35: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/35.jpg)
136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8Chemical Shift (ppm)
126.05 114.62 110.99 84.14 77.09 76.77 24.77 24.57 9.71 3.47
S27.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C8H8NBpin] (O)
NBO
O
![Page 36: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/36.jpg)
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
13.900.250.802.030.240.121.001.000.190.900.09
7.27 5.82 5.79 5.09 4.95 3.45 3.44 2.26 1.79 1.17 1.14 0.00
S28.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C3H5N(H)Bpin] (P)
NH
BO
O
![Page 37: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/37.jpg)
55 50 45 40 35 30 25 20 15 10 5Chemical Shift (ppm)
24.35
S29.11B NMR spectrum (128.4 MHz, 25°C, CDCl3 of [C3H5N(H)Bpin] (P)
NH
BO
O
![Page 38: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/38.jpg)
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)
139.07 112.93 81.93 77.07 43.46 24.46
S30.13C NMR spectrum (100 MHz, 25°C, CDCl3 of [C3H5N(H)Bpin] (P)
NH
BO
O
![Page 39: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/39.jpg)
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.062.005.152.00
3.02 3.00 1.69 1.68 0.99 0.97 0.00
S31.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [(CH3)2NBR2] (Q)
N B
![Page 40: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/40.jpg)
75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
47.71
S32.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [(CH3)2NBR2] (Q)
N B
![Page 41: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/41.jpg)
9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
2.087.892.00
7.26 3.28 3.26 1.79 1.77 1.35 0.07
S33.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [(CH2)4NBR2] (R)
N B
![Page 42: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/42.jpg)
75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
48.43
S34.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [(CH2)4NBR2] (R)
N B
![Page 43: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/43.jpg)
9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
1.232.361.9916.531.960.952.075.021.22
6.95 6.92 4.55 3.61 1.76 1.75 1.32 0.00
S35.1H NMR spectrum (400 MHz, 25°C, CDCl3) of [C6H4FN(H)BR2] (U)
HN B
F
![Page 44: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/44.jpg)
75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
52.81 27.66
S36.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of [C6H4FN(H)BR2] (U)
HN B
F
![Page 45: Supporting Information for - rsc.org · Supporting Information for Alkali Metal Catalyzed Dehydro-coupling of Boranes and Amines Leading to the Formation of B-N Bond A. Harinath,a](https://reader031.vdocument.in/reader031/viewer/2022022117/5c9f153b88c993502d8cb856/html5/thumbnails/45.jpg)