The Journal of Organic Chemistry
Page 6 of 10
1
2
3
4
5
6
7
8
9
P= 21.3 Hz), 108.6 (d, CH=, cod, JC-P= 14.1 Hz), 117.8-145.3 (aro-
cod, JC-P= 20.5 Hz), 107.9 (d, CH=, cod, JC-P= 14.3 Hz), 117.4-149.7
matic carbons), 162.1 (q, C-B, BArF, 1JC-B= 49.9 Hz). Minor isomer
(aromatic carbons), 161.6 (q, C-B, BArF, 1JC-B= 49.7 Hz). Minor iso-
(20%): 31P NMR (161.9 MHz, CDCl3): δ = 119.3 (s). 1H NMR (400
mer (22%): 31P NMR (161.9 MHz, CDCl3): δ = 118.6 (s). 1H NMR
t
t
t
MHz, CDCl3): δ = 1.28 (s, 9H, CH3, Bu), 1.57 (s, 9H, CH3, Bu),
1.70 (s, 3H, CH3), 1.73-1.93 (m, 4H, CH2, cod), 1.96 (s, 3H, CH3),
2.00-2.30 (m, 4H, CH2, cod), 2.30 (s, 3H, CH3), 2.34 (s, 3H, CH3),
3.54 (s, 3H, CH3), 4.10 (m, 1H, CH=, cod), 4.14 (m, 1H, CH=,
cod), 4.74 (m, 1H, CH=, cod), 5.89 (m, 1H, CH=, cod), 6.46-7.80
(m, 23H, CH=). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 16.8
(CH3), 16.9 (CH3), 20.7 (CH3), 20.9 (CH3), 25.8 (CH2, cod), 30.4
(CH2, cod), 31.4 (CH3, tBu), 31.5 (CH3, tBu), 31.9 (CH2, cod), 32.3
(400 MHz, CDCl3): δ = 1.01 (s, 9H, CH3, Bu), 1.14-1.25 (m, 3H,
t
t
CH2, cod), 1.28 (s, 9H, CH3, Bu), 1.33 (s, 9H, CH3, Bu), 1.38 (s,
9H, CH3, tBu), 1.46 (s, 9H, CH3, tBu), 1.59 (s, 9H, CH3, tBu), 2.08-
2.15 (m, 3H, CH2, cod), 2.32-2.45 (m, 2H, CH2, cod), 2.60 (m, 1H,
CH=, cod), 3.97 (s, 3H, CH3), 4.49 (m, 1H, CH=, cod), 5.72 (m,
1H, CH=, cod), 6.36 (m, 1H, CH=, cod), 6.39-7.81 (m, 23H, CH=).
13C{1H} NMR (100.6 MHz, CDCl3): δ = 22.6 (CH2, cod), 25.7
(CH2, cod), 29.5 (CH2, cod), 29.7 (CH3, tBu), 30.8 (CH3, tBu), 31.4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
t
t
t
t
t
(CH2, cod), 35.8 (C, Bu), 44.6 (CH3), 53.8 (CH=, cod), 63.1
(CH3, Bu), 31.6 (CH3, Bu), 34.4 (C, Bu), 34.9 (C, Bu), 35.2 (C,
(CH=, cod), 100.0 (CH=, cod), 109.0 (d, CH=, cod, JC-P= 14.4 Hz),
121.8-147.3 (aromatic carbons), 162.1 (q, C-B, BArF, 1JC-B= 49.9
Hz). HRMS (ESI-TOF) m/z: [M- BArF]+ Calcd for C45H61IrNO4PS
930.3297; Found 930.3293.
tBu), 35.5 (C, tBu), 35.6 (C, tBu), 36.5 (CH2, cod), 49.5 (CH3), 55.4
(CH=, cod), 68.1 (CH=, cod), 103.3 (CH=, cod), 109.0 (CH=,
1
cod), 1204-149.7 (aromatic carbons), 161.6 (q, C-B, BArF, JC-B
=
49.7 Hz). HRMS (ESI-TOF) m/z: [M- BArF]+ Calcd for
C57H80IrNO4PS 1098.5175; Found 1098.5170 .
[Ir(cod)(L1c)]BArF. Yield: 126 mg (95%). Major isomer
(80%): 31P NMR (161.9 MHz, CDCl3): δ = 121.4 (s). 1H NMR (400
MHz, CDCl3): δ =1.17-1.28 (m, 2H, CH2, cod), 1.26 (s, 9H, CH3,
[Ir(cod)(L3a)]BArF. Yield: 125 mg (91%). 31P NMR (161.9
MHz, CDCl3): δ = 116.2 (s). 1H NMR (400 MHz, CDCl3): δ = 1.26-
1.28 (m, 1H, CH2, cod), 1.38 (s, 18H, CH3, tBu), 1.42 (s, 9H, CH3,
tBu), 1.49 (s, 9H, CH3, tBu), 1.66-1.68 (m, 1H, CH2, cod), 1.92-2.10
(m, 3H, CH2, cod), 2.18-2.27 (m, 2H, CH2, cod), 2.43-2.46 (m, 1H,
CH2, cod), 3.08 (m, 1H, CH=, cod), 3.54 (m, 1H, CH=, cod), 5.80
(m, 1H, CH=, cod), 6.49 (m, 1H, CH=, cod), 6.68-7.71 (m, 26H,
CH=). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 26.2 (CH2, cod),
28.6 (CH2, cod), 29.7 (CH2, cod), 31.3 (CH3, tBu), 31.5 (CH3, tBu),
t
tBu), 1.54 (m, 1H, CH=, cod), 1.69 (s, 9H, CH3, Bu), 1.74 (s, 3H,
CH3), 1.90-2.13 (m, 2H, CH2, cod), 2.21-2.29 (m, 2H, CH2, cod),
2.40-2.44 (m, 2H, CH2, cod), 1.98 (s, 3H, CH3), 2.31 (s, 3H, CH3),
2.36 (s, 3H, CH3), 3.87 (s, 3H, CH3), 4.06 (m, 1H, CH=, cod), 5.31
(m, 1H, CH=, cod), 6.11 (m, 1H, CH=, cod), 6.53-8.50 (m, 23H,
CH=). 13C{1H} NMR (100.6 MHz, CDCl3): δ =16.4 (CH3), 16.5
(CH3), 20.2 (CH3), 20.5 (CH3), 25.2 (CH2, cod), 29.6 (CH2, cod),
31.0 (CH3, Bu), 31.1 (CH3, Bu), 32.1 (CH2, cod), 34.7 (C, Bu),
34.8 (C, tBu), 36.8 (CH2, cod), 49.5 (CH3), 55.1 (CH=, cod), 68.8
(CH=, cod), 99.6 (d, CH=, cod, JC-P= 21.3 Hz), 108.0 (d, CH=, cod,
32.2 (CH3, tBu), 34.8 (d, C, tBu, JC-P= 4.2 Hz), 35.6 (d, C, tBu, JC-P
=
t
t
t
7.1 Hz), 36.2 (CH2, cod), 56.7 (CH=, cod), 61.6 (CH=, cod), 107.8
(d, CH=, cod, JC-P= 16.9 Hz), 110.7 (d, CH=, cod, JC-P= 14.1 Hz),
116.1 (CH=), 117.5-149.1 (aromatic carbons), 161.7 (q, C-B, BArF,
1JC-B= 49.8 Hz). HRMS (ESI-TOF) m/z: [M- BArF]+ Calcd for
C50H62IrNO4PS 996.3766; Found 996.3762.
J
C-P= 14.1 Hz), 117.4-144.9 (aromatic carbons), 161.6 (q, C-B, BArF,
1JC-B= 49.9 Hz). Minor isomer (20%): 31P NMR (161.9 MHz,
CDCl3): δ = 119.1 (s). 1H NMR (400 MHz, CDCl3): δ = 1.00-1.11
(m, 2H, CH2, cod), 1.11 (s, 9H, CH3, tBu), 1.22-1.25 (m, 2H, CH2,
cod), 1.56 (s, 9H, CH3, tBu), 1.68-1.72 (m, 1H, CH2, cod), 1.85 (s,
3H, CH3), 2.10-2.21 (m, 3H, CH2, cod), 2.24 (s, 3H, CH3), 2.32 (s,
6H, CH3), 3.08 (s, 3H, CH3), 3.89 (m, 1H, CH=, cod), 4.26 (m, 1H,
CH=, cod), 4.43 (m, 1H, CH=, cod), 6.05 (m, 1H, CH=, cod), 6.96-
7.93 (m, 23H, CH=). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 16.4
(CH3), 20.2 (CH3), 20.4 (CH3), 25.5 (CH2, cod), 28.2 (CH2, cod),
[Ir(cod)(L3b)]BArF. Yield: 124 mg (94%). 31P NMR (161.9
MHz, CDCl3): δ = 113.7 (s). 1H NMR (400 MHz, CDCl3): δ = 1.28
t
t
(m, 1H, CH2, cod), 1.36 (s, 9H, CH3, Bu), 1.45 (s, 9H, CH3, Bu),
1.79 (s, 3H, CH3), 1.73-1.95 (m, 2H, CH2, cod), 1.85 (s, 3H, CH3),
2.13-2.22 (m, 3H, CH2, cod), 2.30 (s, 3H, CH3), 2.31 (s, 3H, CH3),
2.42 (m, 1H, CH2, cod), 3.02 (m, 1H, CH=, cod), 3.59 (m, 1H,
CH=, cod), 5.76 (m, 1H, CH=, cod), 6.39 (m, 1H, CH=, cod), 6.66-
7.73 (m, 26H, CH=). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 16.5
(CH3), 16.6 (CH3), 20.4 (CH3), 26.1 (CH2, cod), 28.6 (CH2, cod),
t
t
29.3 (CH2, cod), 30.9 (CH3, Bu), 31.7 (CH2, cod), 34.9 (C, Bu),
35.3 (C, tBu), 36.8 (CH2, cod), 44.1 (CH3), 54.4 (CH=, cod), 68.4
(CH=, cod), 99.6 (CH=, cod), 108.3 (d, CH=, cod, JC-P= 21.5 Hz),
121.2-146.8 (aromatic carbons), 161.6 (q, C-B, BArF, 1JC-B= 49.9
Hz). HRMS (ESI-TOF) m/z: [M- BArF]+ Calcd for C45H56IrNO4PS
930.3297; Found 930.3294.
t
t
t
31.2 (CH2, cod) 31.6 (CH3, Bu), 32.4 (CH3, Bu), 34.9 (C, Bu),
35.0 (C, tBu), 36.2 (CH2, cod), 56.8 (CH=, cod), 62.1 (CH=, cod),
107.4 (d, CH=, cod, JC-P= 14.8 Hz), 109.4 (d, CH=, cod, JC-P= 17.8
Hz), 115.8 (CH=), 117.5-144.7 (aromatic carbons), 161.6 (q, C-B,
BArF, 1JC-B= 49.8 Hz). HRMS (ESI-TOF) m/z: [M- BArF]+ Calcd for
C46H54IrNO4PS 940.3140; Found: 940.3138.
[Ir(cod)(L2a)]BArF. Yield: 138 mg (95%). Major isomer
(78%): 31P NMR (161.9 MHz, CDCl3): δ = 117.4 (s). 1H NMR (400
t
t
MHz, CDCl3): δ = 1.15 (s, 9H, CH3, Bu), 1.17 (s, 9H, CH3, Bu),
General procedure for the asymmetric hydrogenation. The al-
kene (0.25 mmol) and Ir complex (1 mol%) were dissolved in
CH2Cl2 (1.5 mL) and placed in a high-pressure autoclave. The auto-
clave was purged 4 times with hydrogen. Then, it was pressurized at
the desired pressure. After the desired reaction time, the autoclave
was depressurized, and the solvent evaporated off. The residue was
dissolved in Et2O (1.5 ml) and filtered through a short plug of Celite.
Conversions were determined by 1H NMR and enantiomeric ex-
cesses were determined by chiral HPLC or GC.
t
t
1.31 (s, 9H, CH3, Bu), 1.37 (s, 9H, CH3, Bu), 1.40 (s, 9H, CH3,
tBu), 1.70 (m, 1H, CH2, cod), 1.74 (s, 9H, CH3, tBu), 1.92-2.00 (m,
3H, CH2, cod), 2.03 (m, 1H, CH=, cod), 2.30-2.34 (m, 2H, CH2,
cod), 2.40-2.58 (m, 2H, CH2, cod), 2.90 (s, 3H, CH3), 3.97 (m, 1H,
CH=, cod), 4.63 (m, 1H, CH=, cod), 6.20 (m, 1H, CH=, cod), 7.02-
8.43 (m, 23H, CH=). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 22.7
(CH2, cod), 24.7 (CH2, cod), 30.0 (CH2, cod), 30.6 (CH3, tBu), 31.0
(CH3, tBu), 31.3 (CH3, tBu), 31.9 (CH3, tBu), 34.4 (C, tBu), 34.8 (C,
t
t
t
tBu), 34.9 (C, Bu), 35.1 (C, Bu), 35.5 (C, Bu), 35.9 (CH2, cod),
43.3 (CH3), 52.7 (CH=, cod), 66.4 (CH=, cod), 101.3 (d, CH=,
ACS Paragon Plus Environment