Catalysts for Asymmetric FLP Hydrogenations Chiral Carbene ... · Catalysts for Asymmetric FLP...

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