catalysts for asymmetric flp hydrogenations chiral carbene ... · catalysts for asymmetric flp...
TRANSCRIPT
Chiral Carbene–Borane Adducts: Precursors for Borenium Catalysts for Asymmetric FLP Hydrogenations
Jolie Lam,a Benjamin A. R. Günther,ab Jeffrey M. Farrell,a Patrick Eisenberger*,c Brian P. Bestvater,c Paul D. Newman,b Rebecca L. Melen,*b Cathleen M. Crudden,*cd Douglas W. Stephan*a
Supporting Information
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016
Table of Contents1H NMR (500 MHz, CDCl3, 298 K) spectrum of 2 113C NMR (126 MHz, CDCl3, 298 K) spectrum of 2 11H NMR (500 MHz, CD3CN, 298 K) spectrum of 3 213C NMR (126 MHz, CD3CN, 298 K) spectrum of 3 21H NMR (500 MHz, CDCl3, 298 K) spectrum of 4 313C NMR (126 MHz, CDCl3, 298 K) spectrum of 4 31H NMR (500 MHz, CDCl3, 298 K) spectrum of 5 413C NMR (126 MHz, CDCl3, 298 K) spectrum of 5 41H NMR (500 MHz, CDCl3, 298 K) spectrum of 6 513C NMR (126 MHz, CDCl3, 298 K) spectrum of 6 51H NMR (400 MHz, CD2Cl2, 298 K) spectrum of 7 613C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 7 619F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 7 711B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 7 71H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 8 813C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 8 819F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 8 911B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 8 91H NMR (400 MHz, C6D6, 298 K) spectrum of 9 1013C NMR (126 MHz, C6D6, 298 K) spectrum of 9 1011B NMR (128 MHz, C6D6, 298 K) spectrum of 9 111H NMR (500 MHz, C6D6, 298 K) spectrum of 10 1213C NMR (126 MHz, C6D6, 298 K) spectrum of 10 1211B NMR (128 MHz, C6D6, 298 K) spectrum of 10 131H NMR (500 MHz, C6D6, 298 K) spectrum of 11 1413C NMR (126 MHz, C6D6, 298 K) spectrum of 11 1411B NMR (128 MHz, C6D6, 298 K) spectrum of 11 151H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 12 1613C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 12 1619F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 12 1711B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 12 171H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 13 18
13C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 13 1819F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 13 1911B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 13 191H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 14 2013C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 14 2019F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 14 2111B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 14 211H NMR (500 MHz, C6D6, 298 K) spectrum of 15 2213C NMR (126 MHz, C6D6, 298 K) spectrum of 15 2211B NMR (128 MHz, C6D6, 298 K) spectrum of 15 231H NMR (500 MHz, C6D6, 298 K) spectrum of 16 2413C NMR (126 MHz, C6D6, 298 K) spectrum of 16 2411B NMR (128 MHz, C6D6, 298 K) spectrum of 16 251H NMR (500 MHz, C6D6, 298 K) spectrum of 17 2613C NMR (126 MHz, C6D6, 298 K) spectrum of 17 2611B NMR (128 MHz, C6D6, 298 K) spectrum of 17 271H NMR (400 MHz, C6D6, 298 K) spectrum of 20 2813C NMR (125 MHz, C6D6, 298 K) spectrum of 20 2811B NMR (128 MHz, C6D6, 298 K) spectrum of 20 291H NMR (400 MHz, C6D6, 298 K) spectrum of 21 3013C NMR (125 MHz, C6D6, 298 K) spectrum of 21 3011B NMR (128 MHz, C6D6, 298 K) spectrum of 21 311H NMR (400 MHz, C6D6, 298 K) spectrum of 22 3213C NMR (125 MHz, C6D6, 298 K) spectrum of 22 3211B NMR (128 MHz, C6D6, 298 K) spectrum of 22 331H NMR (400 MHz, C6D6, 298 K) spectrum of 23 3413C NMR (125 MHz, C6D6, 298 K) spectrum of 23 3411B NMR (128 MHz, C6D6, 298 K) spectrum of 23 351H NMR (400 MHz, CDCl3, 298 K) spectrum of 24 3613C NMR (125 MHz, CDCl3, 298 K) spectrum of 24 3611B NMR (128 MHz, d8-toluene, 298 K) spectrum of 24 371H NMR (400 MHz, CDCl3, 298 K) spectrum of 25 3813C NMR (125 MHz, CDCl3, 298 K) spectrum of 25 38
11B NMR (128 MHz, d8-toluene, 298 K) spectrum of 25 391H NMR (400 MHz, CD2Cl2, 298 K) spectrum of 26 4013C NMR (125 MHz, CDCl3, 298 K) spectrum of 26 4011B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 26 411H NMR (400 MHz, CDCl3, 298 K) spectrum of 27 4213C NMR (125 MHz, CD2Cl2, 298 K) spectrum of 27 4211B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 27 431H NMR (400 MHz, CD2Cl2, 298 K) spectrum of 28 4413C NMR (125 MHz, CDCl3, 298 K) spectrum of 28 4411B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 28 451H NMR (600 MHz, C6D6, 298 K) spectrum of 29 4613C NMR (125 MHz, C6D6, 298 K) spectrum of 29 4611B NMR (128 MHz, C6D6, 298 K) spectrum of 29 471H NMR (400 MHz, CDCl3, 298 K) spectrum of 30 4813C NMR (100 MHz, CDCl3, 298 K) spectrum of 30 481H NMR (500 MHz, CDCl3, 298 K) spectrum of 31 4913C NMR (100 MHz, CDCl3, 298 K) spectrum of 31 491H NMR (400 MHz, CDCl3, 298 K) spectrum of 32 501H NMR (500 MHz, CDCl3, 298 K) spectrum of 33 5113C NMR (125 MHz, CDCl3, 298 K) spectrum of 33 511H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 34a 5213C NMR (125 MHz, CD2Cl2, 298 K) spectrum of 34a 5211B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 34a 53
Table for catalytic hydrogenations of 20, 21, 23, 24, 25, 26, 27, 28, and 34 54
S1
1H NMR (500 MHz, CDCl3, 298 K) spectrum of 2
0.40.50.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.2f1 (ppm)
6.20
3.33
4.96
2.26
1.06
1.00
0.78
0.79
1.01
1.30
1.35
1.61
2.01
2.95
2.97
2.99
13C NMR (126 MHz, CDCl3, 298 K) spectrum of 2
510152025303540455055606570758085f1 (ppm)
16.4
1
22.3
7
26.0
1
30.4
5
38.4
9
46.3
1
60.9
661
.14
76.9
177
.16
77.4
1
NH2NH2
NH2NH2
S2
1H NMR (500 MHz, CD3CN, 298 K) spectrum of 3
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
2.92
3.04
3.00
3.16
1.06
0.89
1.00
1.42
0.98
1.11
1.22
2.02
2.17
2.29
2.35
3.41
3.42
7.61
7.83
13C NMR (126 MHz, CD3CN, 298 K) spectrum of 3
0102030405060708090100110120130140150f1 (ppm)
16.1
616
.85
20.5
9
34.0
2
39.5
042
.66
62.4
8
66.6
0
152.
44
NNH
HBF4
NNH
HBF4
S3
1H NMR (500 MHz, CDCl3, 298 K) spectrum of 4
0.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.53.63.7f1 (ppm)
2.95
3.00
2.97
1.00
1.09
0.98
0.98
0.96
2.92
2.92
1.07
1.12
1.26
1.86
1.87
1.88
1.90
1.91
1.92
2.05
2.08
2.12
2.29
2.32
2.35
2.51
2.54
2.57
3.13
3.14
3.22
3.30
13C NMR (126 MHz, CDCl3, 298 K) spectrum of 4
5101520253035404550556065707580859095100105110115120125130135140145150155f1 (ppm)
14.2
316
.93
21.7
6
30.6
3
36.9
838
.51
40.7
841
.15
68.8
169
.46
153.
74
NN BF4
NN BF4
S4
1H NMR (500 MHz, CDCl3, 298 K) spectrum of 5
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
2.90
2.92
2.97
2.98
3.46
1.04
0.99
0.96
0.96
0.94
1.07
1.02
1.04
1.03
1.00
1.03
1.15
1.30
1.34
1.38
1.98
2.14
2.29
2.52
3.19
3.20
3.57
3.66
3.73
3.82
9.05
13C NMR (126 MHz, CDCl3, 298 K) spectrum of 5
102030405060708090100110120130140150160f1 (ppm)
14.0
814
.33
17.1
717
.29
21.8
6
32.1
1
40.6
540
.85
45.2
648
.75
66.2
8
69.9
3
153.
15
NN BF4
NN BF4
S5
1H NMR (500 MHz, CDCl3, 298 K) spectrum of 6
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
2.84
2.98
3.00
3.05
3.07
2.93
3.05
0.99
2.03
0.97
1.04
1.02
1.00
1.00
0.97
1.17
1.37
1.54
1.64
2.01
2.13
2.19
2.44
3.31
3.94
4.95
9.00
13C NMR (126 MHz, CDCl3, 298 K) spectrum of 6
101520253035404550556065707580859095100105110115120125130135140145150155f1 (ppm)
14.8
617
.71
20.6
821
.69
22.2
123
.56
25.0
8
33.4
5
40.3
941
.13
51.1
0
55.9
5
61.3
7
71.4
9
151.
11
NN
BF4
NN
BF4
S6
1H NMR (400 MHz, CD2Cl2, 298 K) spectrum of 7
1.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.1f1 (ppm)
6.06
2.97
1.35
2.35
1.57
2.95
1.10
3.00
1.06
1.07
1.16
1.81
2.07
2.41
2.83
2.94
3.07
13C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 7
101520253035404550556065707580859095100105110115120125130135140145150155f1 (ppm)
15.4
616
.84
22.8
4
29.6
3
36.3
936
.92
39.3
141
.62
42.2
6
70.6
571
.54
136.
3513
8.24
140.
20
147.
4814
9.43
153.
63
NN
BH
C6F5
C6F5
NN
BH
C6F5
C6F5
S7
19F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 7
-171-169-167-165-163-161-159-157-155-153-151-149-147-145-143-141-139-137-135-133-131f1 (ppm)
-165
.57
-161
.57
-134
.71
-133
.27
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 7
-50-40-30-20-100102030405060708090100110120130f1 (ppm)
-23.
81-2
3.12
NN
BH
C6F5
C6F5
NN
BH
C6F5
C6F5
S8
1H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 8
0.50.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.5f1 (ppm)
1.20
1.25
1.39
2.08
2.17
2.30
2.35
2.56
2.63
2.97
3.02
3.15
3.21
3.27
3.28
13C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 8
5101520253035404550556065707580859095100105110115120125130135140145150155f1 (ppm)
13.7
616
.06
21.0
122
.30
30.9
834
.09
37.1
938
.85
69.1
3
123.
2912
5.17
128.
1012
8.91
130.
5513
5.26
137.
1913
9.12
139.
8614
2.58
143.
5214
7.14
148.
9915
1.85
NN
BC6F5
C6F5
[B(C6F5)4]
NN
BC6F5
C6F5
[B(C6F5)4]
S9
19F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 8
-170-168-166-164-162-160-158-156-154-152-150-148-146-144-142-140-138-136-134-132-130-128-126-124-122-120-118-116-114f1 (ppm)
-167
.63
-163
.73
-157
.35
-156
.33
-137
.90
-133
.19
-130
.71
-126
.06
-124
.09
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 8
-50-40-30-20-100102030405060708090100110120130f1 (ppm)
-16.
68
56.0
4
NN
BC6F5
C6F5
[B(C6F5)4]
NN
BC6F5
C6F5
[B(C6F5)4]
S10
1H NMR (400 MHz, C6D6, 298 K) spectrum of 9
0.30.40.50.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.1f1 (ppm)
2.81
3.00
2.85
0.68
1.36
2.81
1.16
3.24
3.06
2.90
1.81
2.15
2.45
5.31
13C NMR (126 MHz, C6D6, 298 K) spectrum of 9
1520253035404550556065707580f1 (ppm)
15.0
416
.63
21.8
0
28.3
730
.53
30.8
5
34.1
935
.20
38.3
338
.54
40.1
140
.99
68.7
069
.83
NN
BH
NN
BH
S11
11B NMR (128 MHz, C6D6, 298 K) spectrum of 9
-50-40-30-20-100102030405060708090100110120130f1 (ppm)
-14.
50-1
3.86
NN
BH
S12
1H NMR (500 MHz, C6D6, 298 K) spectrum of 10
0.40.50.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.53.63.73.83.94.04.14.24.34.44.5f1 (ppm)
3.01
3.00
3.00
3.28
3.08
1.76
1.43
3.14
1.95
3.16
2.24
2.76
1.10
1.14
1.16
1.14
13C NMR (126 MHz, C6D6, 298 K) spectrum of 10
101520253035404550556065707580859095100105110115120125130f1 (ppm)
14.6
015
.95
17.3
618
.45
21.9
223
.54
25.5
230
.89
31.0
331
.28
39.0
239
.27
39.5
539
.90
42.0
3
47.5
2
66.5
868
.53
NN
BH
NN
BH
S13
11B NMR (128 MHz, C6D6, 298 K) spectrum of 10
-90-80-70-60-50-40-30-20-100102030405060708090f1 (ppm)
-14.
62-1
3.96
NN
BH
S14
1H NMR (500 MHz, C6D6, 298 K) spectrum of 11
0.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.6f1 (ppm)
3.01
3.00
3.07
5.92
3.00
3.82
3.66
3.12
3.40
2.68
1.35
1.15
1.14
13C NMR (126 MHz, C6D6, 298 K) spectrum of 11
20253035404550556065707580859095100105110115120125130f1 (ppm)
18.0
718
.31
20.3
420
.86
21.6
922
.58
24.5
925
.44
25.8
330
.77
32.1
332
.84
37.6
739
.73
40.5
140
.64
49.9
3
52.7
6
59.8
0
69.6
6
NN
BH
NN
BH
S15
11B NMR (128 MHz, C6D6, 298 K) spectrum of 11
-50-40-30-20-100102030405060708090100110120130f1 (ppm)
-13.
18-1
2.51
NN
BH
S16
1H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 12
0.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.5f1 (ppm)
2.44
1.29
6.60
2.27
4.24
1.54
2.98
2.80
1.00
1.15
1.20
1.39
1.74
1.90
2.03
2.06
2.22
2.36
2.45
2.98
3.10
3.19
3.20
13C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 12
2030405060708090100110120130140150160170f1 (ppm)
14.4
117
.01
21.8
022
.88
30.6
930
.82
31.2
132
.44
33.2
536
.49
36.7
437
.37
38.0
138
.91
40.9
842
.30
71.0
571
.19
124.
0312
4.35
124.
3712
4.90
126.
8612
8.86
129.
5312
9.91
135.
9213
7.82
139.
79
147.
7614
9.67
173.
20
NN
B
[B(C6F5)4]
NN
B
[B(C6F5)4]
S17
19F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 12
-174-172-170-168-166-164-162-160-158-156-154-152-150-148-146-144-142-140-138-136-134-132-130-128f1 (ppm)
-167
.61
-163
.76
-133
.16
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 12
-50-40-30-20-100102030405060708090100110120130f1 (ppm)
-16.
65
89.4
8
NN
B
[B(C6F5)4]
NN
B
[B(C6F5)4]
S18
1H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 13
1.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.53.63.7f1 (ppm)
2.72
2.87
3.07
3.23
2.92
2.38
1.16
5.51
0.80
0.95
1.45
5.30
1.07
1.00
1.03
2.01
1.00
1.07
1.18
1.27
1.28
1.30
1.37
1.38
1.39
1.42
1.69
1.82
1.97
2.14
2.26
2.33
2.46
2.77
3.09
3.24
3.52
13C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 13
81012141618202224262830323436384042444648505254565860626466687072f1 (ppm)
14.3
914
.66
17.4
917
.89
21.7
222
.72
22.8
5
31.9
932
.39
32.5
9
36.7
037
.01
37.2
537
.42
40.8
741
.16
47.7
5
49.9
0
67.3
0
70.7
6
NN
B
[B(C6F5)4]
NN
B
[B(C6F5)4]
S19
19F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 13
-176-174-172-170-168-166-164-162-160-158-156-154-152-150-148-146-144-142-140-138-136-134-132-130-128-126f1 (ppm)
-167
.58
-163
.73
-133
.12
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 13
-50-40-30-20-100102030405060708090100110120130f1 (ppm)
-16.
65
89.1
1
NN
B
[B(C6F5)4]
NN
B
[B(C6F5)4]
S20
1H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 14
1.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.5f1 (ppm)
3.07
3.04
2.81
2.73
2.69
2.62
2.75
6.16
2.72
8.57
1.15
1.00
0.87
0.75
1.10
1.16
1.26
1.28
1.34
1.35
1.46
1.47
1.54
1.61
1.62
1.64
1.84
1.85
1.88
1.89
1.92
1.93
2.04
2.05
2.07
2.08
2.10
2.11
2.14
2.24
2.25
2.27
2.28
2.31
2.34
2.59
2.69
3.11
3.32
3.33
13C NMR (126 MHz, CD2Cl2, 298 K) spectrum of 14
10121416182022242628303234363840424446485052545658606264666870727476f1 (ppm)
17.7
418
.10
20.9
221
.32
21.7
722
.63
22.8
222
.92
24.2
3
34.2
836
.60
36.8
537
.59
37.6
5
41.2
141
.94
57.3
6
61.2
662
.50
72.9
8
NN
B
[B(C6F5)4]
NN
B
[B(C6F5)4]
S21
19F NMR (377 MHz, CD2Cl2, 298 K) spectrum of 14
-174-172-170-168-166-164-162-160-158-156-154-152-150-148-146-144-142-140-138-136-134-132-130-128f1 (ppm)
-167
.61
-163
.79
-133
.11
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 14
-50-40-30-20-100102030405060708090100110120130f1 (ppm)
-16.
65
85.8
4
NN
B
[B(C6F5)4]
NN
B
[B(C6F5)4]
S22
1H NMR (500 MHz, C6D6, 298 K) spectrum of 15
0.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.7f1 (ppm)
0.74
0.92
1.11
1.32
1.37
1.45
1.49
1.52
1.56
1.65
1.72
1.76
1.81
1.85
2.13
2.19
2.34
2.49
2.54
2.57
2.58
2.60
2.63
13C NMR (126 MHz, C6D6, 298 K) spectrum of 15
20253035404550556065707580859095100105110115120125f1 (ppm)
20.5
622
.18
24.6
925
.45
26.3
429
.10
29.3
631
.15
39.0
739
.37
40.2
442
.77
44.5
5
51.8
8
66.6
567
.50
79.2
5
NN
B
H
NN
B
H
S23
11B NMR (128 MHz, C6D6, 298 K) spectrum of 15
-20-15-10-505101520253035404550f1 (ppm)
44.2
4
NN
B
H
S24
1H NMR (500 MHz, C6D6, 298 K) spectrum of 16
0.20.30.40.50.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.3f1 (ppm)
0.63
0.68
0.74
1.02
1.04
1.19
1.23
1.41
1.50
1.59
1.65
1.75
1.79
1.95
2.07
2.26
2.39
2.46
2.47
2.51
3.03
3.17
13C NMR (126 MHz, C6D6, 298 K) spectrum of 16
12141618202224262830323436384042444648505254565860626466687072747678f1 (ppm)
14.3
415
.68
15.8
417
.09
18.1
920
.43
21.4
321
.65
22.3
723
.27
25.4
725
.62
26.6
928
.55
29.8
030
.63
30.6
930
.75
31.0
231
.48
37.6
338
.76
39.0
039
.30
39.6
341
.77
42.5
2
46.1
946
.88
47.2
6
50.3
7
51.9
1
66.3
068
.23
68.6
8
76.2
2
NN
B
H
NN
B
H
S25
11B NMR (128 MHz, C6D6, 298 K) spectrum of 16
-20-15-10-50510152025303540455055f1 (ppm)
44.2
9
NN
B
H
S26
1H NMR (500 MHz, C6D6, 298 K) spectrum of 17
0.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.53.63.73.83.94.0f1 (ppm)
0.68
0.79
0.80
0.82
0.93
0.95
1.15
1.17
1.19
1.43
1.49
1.60
1.64
1.68
1.74
1.84
1.91
1.99
2.20
2.26
2.86
2.88
3.25
3.39
3.46
3.84
3.91
13C NMR (126 MHz, C6D6, 298 K) spectrum of 17
2022242628303234363840424446485052545658606264666870f1 (ppm)
20.7
021
.30
21.8
922
.10
23.7
725
.36
25.4
127
.11
28.2
029
.00
31.2
932
.25
33.1
733
.44
42.0
1
47.2
148
.11
48.6
349
.64
66.8
5
70.0
4
NN
B
H
NN
B
H
S27
11B NMR (128 MHz, C6D6, 298 K) spectrum of 17
-25-20-15-10-505101520253035404550f1 (ppm)
44.9
6
NN
B
H
S28
1H NMR (400 MHz, C6D6, 298 K) spectrum of 20
-2-101234567891011121314
6.00
6.00
2.28
4.00
3.57
4.81
4.32
2.17
2.16
2.16
0.43
0.44
0.45
0.47
0.59
0.62
0.63
0.64
1.44
1.45
1.46
1.48
1.90
1.91
1.92
1.92
1.93
1.94
1.95
1.96
1.98
1.99
2.01
2.02
2.04
2.06
2.07
2.09
2.10
2.12
2.13
2.15
2.20
2.21
2.24
2.25
2.28
2.31
2.32
2.43
2.45
2.46
2.48
2.50
2.51
2.53
2.54
2.56
2.58
2.59
2.63
2.64
2.65
2.65
2.66
2.67
2.68
2.69
2.70
2.71
2.72
2.73
2.75
3.71
3.71
3.72
3.73
3.73
3.73
3.73
3.74
3.75
3.75
3.91
3.91
3.93
3.93
4.09
4.09
4.10
4.10
4.11
4.11
4.12
4.12
13C NMR (125 MHz, C6D6, 298 K) spectrum of 20
-100102030405060708090100110120130140150160
14.6
1
18.5
9
25.9
426
.53
30.0
433
.30
33.6
036
.60
37.0
2
62.3
3
75.6
5
123.
99
N
N
O
O
iPr
iPr
BH
N
N
O
O
iPr
iPr
BH
S29
11B NMR (128 MHz, C6D6, 298 K) spectrum of 20
-90-80-70-60-50-40-30-20-100102030405060708090
-16.
90-1
6.25
N
N
O
O
iPr
iPr
BH
S30
1H NMR (400 MHz, C6D6, 298 K) spectrum of 21
-2-101234567891011121314
5.95
6.00
1.19
1.04
0.85
1.25
2.50
2.35
4.25
0.43
0.44
0.45
0.64
0.66
0.66
1.70
1.92
2.12
2.13
2.35
2.86
2.87
2.88
2.88
2.89
2.90
2.91
2.92
2.93
2.94
3.78
3.79
3.80
3.81
3.82
3.95
3.95
3.97
3.97
3.98
3.99
4.00
4.01
13C NMR (125 MHz, C6D6, 298 K) spectrum of 21
-100102030405060708090100110120130140150160170180190200210
14.2
818
.32
22.7
3
28.9
6
61.1
1
76.0
9
N
N
O
O
iPr
iPr
BH3
N
N
O
O
iPr
iPr
BH3
S31
11B NMR (128 MHz, C6D6, 298 K) spectrum of 21
-80-70-60-50-40-30-20-1001020304050607080
-36.
63-3
5.95
-35.
26-3
4.57
N
N
O
O
iPr
iPr
BH3
S32
1H NMR (400 MHz, C6D6, 298 K) spectrum of 22
-2-101234567891011121314
5.98
6.00
12.8
2
7.66
2.15
2.19
2.17
2.17
2.16
0.54
0.55
1.13
1.15
1.16
1.18
1.19
1.21
1.21
1.22
1.22
1.22
1.22
1.23
1.23
1.24
1.24
1.24
1.25
1.25
1.27
1.27
1.29
1.29
1.35
1.38
1.45
1.46
1.47
1.49
1.50
1.52
1.52
1.54
1.57
1.57
1.59
1.60
1.61
1.63
1.64
1.66
1.66
1.69
1.70
1.72
1.73
1.75
1.76
1.90
1.92
1.93
1.96
1.97
1.99
2.01
2.04
2.05
2.05
2.36
2.39
3.00
3.00
3.01
3.02
3.03
3.04
3.68
3.68
3.70
3.70
3.70
3.71
3.72
3.72
3.89
3.89
3.91
3.92
4.54
4.54
4.55
4.55
4.56
4.56
4.56
4.57
13C NMR (125 MHz, C6D6, 298 K) spectrum of 22
-100102030405060708090100110120130140150160170180190200210
14.5
8
18.9
128
.04
28.2
028
.33
28.3
929
.49
29.6
329
.74
30.2
131
.10
31.1
531
.43
32.3
732
.81
64.5
4
75.9
1
N
N
O
O
i-Pr
i-Pr
B CyCy
Cl
N
N
O
O
i-Pr
i-Pr
B CyCy
Cl
S33
11B NMR (128 MHz, C6D6, 298 K) spectrum of 22
-90-80-70-60-50-40-30-20-100102030405060708090
3.02
N
N
O
O
i-Pr
i-Pr
B CyCy
Cl
S34
1H NMR (400 MHz, C6D6, 298 K) spectrum of 23
-2-101234567891011121314
18.0
0
1.11
1.18
1.30
1.33
5.55
1.33
3.50
1.21
2.17
2.15
2.13
0.86
0.87
0.88
0.88
0.89
0.89
0.92
1.17
1.20
1.21
1.21
1.21
1.22
1.22
1.22
1.23
1.23
1.24
1.24
1.26
1.26
1.28
1.29
1.55
1.78
1.80
1.81
1.83
1.84
1.86
1.87
1.97
1.99
2.01
2.12
2.22
2.23
2.25
2.31
2.39
2.42
2.45
2.47
2.48
2.50
2.52
2.53
2.54
2.56
2.57
2.59
2.59
2.60
2.61
2.62
2.63
2.64
2.69
2.72
2.74
2.75
3.77
3.77
3.78
3.79
3.80
4.01
4.02
4.02
4.02
4.04
4.04
4.04
4.15
4.15
4.16
13C NMR (125 MHz, C6D6, 298 K) spectrum of 23
-100102030405060708090100110120130140150160170180190200210
25.8
626
.55
27.5
332
.37
33.1
434
.98
35.2
939
.39
68.3
3
78.6
3
124.
26
N
N
O
O
tBu
tBu
BH
N
N
O
O
tBu
tBu
BH
S35
11B NMR (128 MHz, C6D6, 298 K) spectrum of 23
-90-80-70-60-50-40-30-20-100102030405060708090
-16.
75-1
6.08
N
N
O
O
tBu
tBu
BH
S36
1H NMR (400 MHz, CDCl3, 298 K) spectrum of 24
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.0
2.89
0.97
1.00
1.71
5.79
1.28
2.94
2.83
1.05
1.00
1.13
3.15
2.12
1.16
2.15
1.07
6.05
1.09
1.00
0.59
0.60
0.70
0.72
0.94
0.96
1.08
1.09
1.12
1.12
1.26
1.29
1.30
1.37
1.39
1.40
1.41
1.54
1.56
1.58
1.65
1.66
1.68
1.70
1.72
1.73
1.74
1.86
1.87
1.88
1.89
1.99
2.02
2.09
2.10
2.12
2.13
2.16
2.18
2.19
2.21
2.22
3.88
6.74
6.81
13C NMR (125 MHz, CDCl3, 298 K) spectrum of 24
-100102030405060708090100110120130140150160170180190200210220
23.1
323
.35
23.8
528
.46
28.6
533
.26
33.5
935
.34
36.2
237
.53
37.7
939
.07
39.3
342
.67
43.0
743
.45
44.9
849
.94
50.8
2
120.
0112
1.10
N
NBH
N
NBH
S37
11B NMR (128 MHz, d8-toluene, 298 K) spectrum of 24
-50-40-30-20-100102030405060708090100110120130
-9.4
6-8
.80
N
NBH
S38
1H NMR (400 MHz, CDCl3, 298 K) spectrum of 25
-2-101234567891011121314
2.92
1.00
1.50
2.82
2.83
3.54
3.49
2.62
1.48
2.67
1.51
2.97
2.68
2.99
2.04
1.03
4.22
1.03
1.09
1.10
1.00
1.00
0.48
0.49
0.83
0.85
0.94
0.96
1.06
1.10
1.11
1.12
1.17
1.18
1.35
1.37
1.38
1.45
1.47
1.47
1.59
1.62
1.69
1.71
1.72
1.73
1.74
1.84
1.84
1.85
1.85
1.87
2.08
2.11
2.12
2.25
2.26
2.28
5.10
5.11
5.13
5.15
5.80
5.82
5.84
5.88
6.92
6.92
6.97
6.98
13C NMR (125 MHz, CDCl3, 298 K) spectrum of 25
-100102030405060708090100110120130140150160170180190200210220
23.0
523
.20
23.5
023
.55
23.8
723
.99
24.2
528
.53
32.9
533
.95
35.5
337
.30
39.0
839
.21
42.3
043
.27
43.4
845
.08
49.0
549
.44
50.0
450
.79
115.
5411
5.93
N
NiPr
iPr
BH
N
NiPr
iPr
BH
S39
11B NMR (128 MHz, d8-toluene, 298 K) spectrum of 25
-30-20-100102030405060708090100110120130140
-8.5
4-7
.90
N
NiPr
iPr
BH
S40
1H NMR (400 MHz, CD2Cl2, 298 K) spectrum of 26
-2-1012345678910111213
34.0
0
2.58
0.19
1.41
0.18
0.15
0.50
0.52
0.17
3.53
0.64
0.65
0.69
0.71
0.79
0.86
0.89
1.01
1.02
1.10
1.12
1.27
1.38
1.40
1.55
1.56
1.68
1.74
1.84
1.92
2.01
2.07
2.08
2.19
2.22
3.91
5.15
5.19
5.59
5.64
6.77
6.81
7.27
7.33
13C NMR (125 MHz, CDCl3, 298 K) spectrum of 26
0102030405060708090100110120130140150160170180190200210
23.1
523
.36
23.9
328
.48
28.6
133
.42
33.4
635
.26
36.3
037
.60
39.0
939
.35
42.7
343
.03
43.4
144
.65
49.9
450
.78
52.8
2
77.4
1
119.
7512
0.58
128.
1912
8.54
128.
95
136.
61
N
NBn
BH
N
NBn
BH
S41
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 26
-30-20-100102030405060708090100110120130
-22.
19
-9.4
3-8
.79
N
NBn
BH
S42
1H NMR (400 MHz, CDCl3, 298 K) spectrum of 27
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.013.5
4.89
2.62
10.8
4
8.72
3.54
3.24
1.00
1.11
3.72
0.71
0.73
0.81
0.84
0.88
1.08
1.11
1.54
1.59
1.64
1.71
1.76
1.96
2.04
2.10
4.01
6.90
6.95
6.96
7.42
7.43
13C NMR (125 MHz, CD2Cl2, 298 K) spectrum of 27
0102030405060708090100110120130140150160170180190200210
23.1
823
.75
23.9
128
.55
28.6
933
.28
33.6
435
.33
36.3
538
.29
39.3
739
.55
43.5
343
.67
44.5
150
.29
51.2
4
121.
1712
2.36
128.
3212
8.78
128.
95
140.
55
N
NPh
BH
N
NPh
BH
S43
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 27
-50-40-30-20-100102030405060708090100110120130
-10.
05-9
.43
N
NPh
BH
S44
1H NMR (400 MHz, CD2Cl2, 298 K) spectrum of 28
-2-1012345678910111213
2.67
17.6
0
1.83
2.86
9.00
2.92
1.14
1.06
2.71
0.65
0.82
0.62
0.64
1.03
1.06
1.09
1.11
1.11
1.12
1.15
1.18
1.64
1.68
1.70
1.70
1.73
1.82
2.04
2.06
2.08
2.21
2.22
2.23
2.33
2.37
2.40
3.87
6.73
6.73
7.09
7.09
13C NMR (125 MHz, CDCl3, 298 K) spectrum of 28
-100102030405060708090100110120130140150160170180190200210220
23.3
923
.53
24.2
324
.69
28.3
428
.49
32.1
932
.78
34.0
738
.60
39.4
839
.65
42.6
442
.95
43.1
943
.52
50.2
051
.95
60.9
0
118.
1011
9.46
N
Nt-Bu
BH
N
Nt-Bu
BH
S45
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 28
-35-30-25-20-15-10-5051015202530354045505560657075808590
-7.1
8-6
.50
N
Nt-Bu
BH
S46
1H NMR (600 MHz, C6D6, 298 K) spectrum of 29
13C NMR (125 MHz, C6D6, 298 K) spectrum of 29
NN N PhPh
B HPh
NN N PhPh
B HPh
S47
11B NMR (128 MHz, C6D6, 298 K) spectrum of 29
NN N PhPh
B HPh
S48
1H NMR (400 MHz, CDCl3, 298 K) spectrum of 30
13C NMR (100 MHz, CDCl3, 298 K) spectrum of 30
N3
OMe
N3
OMe
S49
1H NMR (500 MHz, CDCl3, 298 K) spectrum of 31
13C NMR (100 MHz, CDCl3, 298 K) spectrum of 31
N
OMeNN
SiMe3
N
OMeNN
SiMe3
S50
1H NMR (400 MHz, CDCl3, 298 K) spectrum of 32
N
OMeNN
S51
1H NMR (500 MHz, CDCl3, 298 K) spectrum of 33
13C NMR (125 MHz, CDCl3, 298 K) spectrum of 33
N
OMeNN Ph
BF4
N
OMeNN Ph
BF4
S52
1H NMR (500 MHz, CD2Cl2, 298 K) spectrum of 34a
13C NMR (125 MHz, CD2Cl2, 298 K) spectrum of 34a
N
OMeNN Ph
BH
N
OMeNN Ph
BH
S53
11B NMR (128 MHz, CD2Cl2, 298 K) spectrum of 34a
N
OMeNN Ph
BH
S54
Table for catalytic hydrogenations of 20, 21, 23, 24, 25, 26, 27, 28, and 34 5 mol% precursor
+ 5 mol% [Trityl][BArF]
DCM, 102 atm H2
substrate product
Entry Substrate Precursor t (h) Temp. Product Yield (%) e.e.
1 20 24 r.t. 100 72 20 6 r.t. 88 93 20 3 r.t. 50 124 20 12 0 ºC 94 15 20 3 50 ºC 71 86 21 24 r.t. 3 57 21 3 50 ºC 6 78 23 24 r.t. 0 -9 23 48 r.t. 0 -
10 24 4 r.t. 55 1211 24 20 -30 5 2012 24a 24 25 0 -13 24b 24 25 12 1514 25 24 -30 <5 815 26 4 25 47 1316 26 24 25 5 1317 27 20 -30 <5 -18 28 4 25 0 -19 28 20 -30 0 -20
N
34 18 25
HN
100 6
10N
20 6 r.t.HN
0 -
11N
EtO
20 6 r.t.HN
EtO
91 11
12 20c 24 r.t. 0 -13 20c 24 70 ºC 0 -14 21c 24 r.t. 0 -15
O
21c 24 70 ºC
OH
0 -16 20 48 r.t. 0 -
17
O
23 48 r.t.
OH
0 -
Carried out in a toluene, b chlorobenzene, c diethyl ether