Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2015
Supporting information
Pd-Catalyzed Asymmetric Allylic Amination Using Easily Accessible Metallocenyl P,N-Ligands Hongwei Wu,a Fang Xie a Yanlan Wang,a Xiaohu Zhao,a Delong Liub,* and Wanbin Zhanga,b,* a
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. China
b
School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. China
E-mail:
[email protected];
[email protected]
Contents 1. NMR Spectra…………………………………………………………………….S2 2. HPLC Spectra………………………………………………………………......S12
S1
1. NMR spectra: NHBn
7a
3.83 3.80 3.79 3.76
4.42 4.40
4.85 4.83 4.80
whw0728-2-1h
7.45 7.43 7.38 7.38 7.36 7.35 7.34 7.32 7.31 7.29 7.28 7.27 7.26 7.26 7.24 7.23 7.21 7.21 7.20 6.61 6.57 6.36 6.34 6.32 6.30
(E)-N-Benzyl-1,3-diphenylprop-2-en-1-amine(7a): 900
800
700
600
500
400
300
200
100
7.0
6.0
5.5
5.0
4.5 f1 (ppm)
2.00
1.02
0.82
1.08
6.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
8500
51.62
7.5
64.82
whw0728-2-13c
8.0
77.57 77.25 76.93
8.5
143.05 140.55 137.18 132.76 130.67 128.85 128.72 128.65 128.42 127.68 127.61 127.53 127.18 126.65
9.0
1.03
1.76 6.43 3.90 1.09
0
8000 7500 7000 6500 6000 5500 5000 4500 4000 3500 3000 2500 2000 1500 1000 500 0 -500 -1000 160
150
140
130
120
110
100
90
80 f1 (ppm)
S2
70
60
50
40
30
20
10
0
HN
7b 380
2.05 2.00 1.97 1.91 1.88 1.79 1.70 1.58 1.26 1.21 1.18 1.16 1.12 1.12 1.09
2.48 2.47
4.58 4.57
7.41 7.39 7.38 7.38 7.37 7.36 7.35 7.34 7.33 7.30 7.28 7.26 7.26 7.26 6.72 6.68 6.55 6.51 6.42 6.41 6.38 6.37 6.35 6.33 6.31 6.29
whw0728-1h
5.40 5.38
(E)-N-(1,3-Diphenylallyl)cyclohexanamine(7b): 360 340 320 300 280 260 240 220 C (ddd) 6.36 A (m) 7.31
200
B (dd) 6.61
D (d) 5.39
E (d) 4.57
F (d) 2.47
G (m) 1.83
180
H (dt) 1.15
160 140 120 100 80 60 40 20
4.0
3.5 3.0 f1 (ppm)
2.5
2.0
3.56
6.26
0.85
4.5
1.5
1.0
0.5
0.0
-0.5
-1.0
-1.5
26.37 25.31
5.0
34.06 33.88
5.5
-20
53.84
6.0
1.00
0.92
1.12
6.5
62.12
7.0
77.56 77.24 76.92 75.30
whw0728-1-13c
7.5
137.29 133.35 131.85 130.73 130.17 128.78 128.69 127.98 127.54 127.34 126.83 126.63
8.0
143.52
8.5
1.24
7.95 1.29
0
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
-1000
160
150
140
130
120
110
100
90
80 f1 (ppm)
S3
70
60
50
40
30
20
10
N
7c
400
1.83
3.85 3.83
7.48 7.46 7.36 7.35 7.34 7.32 7.29 7.28 7.26 7.23 7.22 7.20 7.18 6.60 6.56 6.51 6.48 6.47 6.45
whw0725-4-1h
2.65 2.54
(E)-1-(1,3-Diphenylallyl)pyrrolidine (7c): 380 360 340 320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20
6.5
5.5
5.0
4.5 4.0 f1 (ppm)
3.5
3.0
2.5
3.81
1.98
1.81
1.00 0.76
6.0
128.90 128.72 127.97 127.79 127.64 126.71
whw0725-4-13c
7.0
2.0
1.5
1.0
0.5
0.0
15000
23.58
7.5
-20
53.32
8.0
77.56 77.24 76.92 74.64
8.5
0.76 0.83
1.34 2.82 2.23 1.04
0
14000 13000 12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 -1000 -2000
150
140
130
120
110
100
90
80 f1 (ppm)
S4
70
60
50
40
30
20
10
N
7d
2.63 2.54 2.42 2.41 2.40 2.38 2.37 2.18
3.80 3.78 3.72 3.71 3.70
7.42 7.41 7.39 7.39 7.36 7.35 7.35 7.34 7.34 7.33 7.33 7.31 7.30 7.28 7.28 7.26 7.26 6.59 6.55
whw0725-2-1h
6.32 6.29 6.28 6.26
(E)-1-(1,3-Diphenylallyl)piperidine (7d): 2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
600
400
200
5.0
4.5 4.0 f1 (ppm)
3.5
3.0
2.5
0.48
-200 2.0
1.5
1.0
0.5
52.42
5.5
0.48 2.22 2.19
1.14 3.53
1.02
6.0
67.38
141.74
whw0725-2-13c
6.5
77.57 77.25 76.93 75.06
7.0
131.80 131.58 128.89 128.74 128.25 127.79 127.54 126.60
7.5
136.95
8.0
1.00
0.72 1.16 3.42 1.13 2.02 1.73
0
8000 7500 7000 6500 6000 5500 5000 4500 4000 3500 3000 2500 2000 1500 1000 500 0 -500 -1000
160
155
150
145
140
135
130
125
120
115
110
105
100
95 90 f1 (ppm)
S5
85
80
75
70
65
60
55
50
45
40
35
30
O N
7e
550
2.56 2.43 2.42 2.40
3.82 3.80 3.74 3.73 3.72
7.44 7.42 7.37 7.36 7.34 7.32 7.30 7.28 7.27 7.24 7.22 7.20
whw0724-1-1h
6.61 6.57 6.35 6.32 6.31 6.28
(E)-4-(1,3-Diphenylallyl)morpholine (7e):
500
450
400
350
300
250
200
150
100
50
5.0
4.5
4.0 f1 (ppm)
3.5
3.0
2.01
-50
2.5
2.0
1.5
1.0
0.5
52.44
5.5
67.38
6.0
1.84
1.03 3.37
1.08
6.5
77.64 77.32 77.00 75.09
141.74
whw0724-1-13c
7.0
131.87 131.56 128.93 128.77 128.29 127.83 127.58 126.64
7.5
136.97
8.0
1.00
8.70
0
4500
4000
3500
3000
2500
2000
1500
1000
500
0
-500 160
155
150
145
140
135
130
125
120
115
110
105
100
95
90 85 f1 (ppm)
S6
80
75
70
65
60
55
50
45
40
35
30
25
20
160
whw0412-1-13c
150
140
130
120
6.0
110
5.5
100
5.0 4.5 f1 (ppm) 4.0
90 80 f1 (ppm)
S7 3.5
70
3.0
60
2.5 2.0
50
1.5
40 28.88 28.45 26.71 26.32
6.5
34.15
7.0
58.52
7.5
70.89
8.0
77.63 77.32 77.00
8.5
137.48 133.30 130.29 128.77 128.73 128.05 127.52 127.14 126.61
9.0
143.71
3.07
4.44 0.85 2.40
3.00
1.07
1.52
1.09
0.98
10.60
whw0412-1-1h
1.56 1.35 1.33 1.30 1.11 1.08 1.05
1.76
2.20
2.61 2.59
4.27 4.24
7.42 7.41 7.37 7.36 7.34 7.33 7.31 7.31 7.29 7.27 7.27 7.26 7.26 7.26 7.26 7.25 7.24 7.24 7.23 7.22 7.22 7.21 7.21 7.20 7.20 7.19 6.55 6.51
N
7f
(E)-N-(1,3-Diphenylallyl)-N-methylcyclohexanamine (7f): 650
600
550
500
450
400
350
300
250
200
150
100
50
0
1.0
30
0.5
20
0.0 -50
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
0
-500
10
whw0728-3-13c
150
140
130
8.0 7.5
120
7.0
110
6.5 6.0
100
5.5
90
5.0 4.5 f1 (ppm)
80 f1 (ppm)
4.0
70
S8 3.5
60
3.0 2.5
50 11.25
8.5
43.31
9.0 6.00
4.27
1.30
1.05
1.10
1.96 1.94 3.76 2.14
1.04 1.02 1.01
2.69 2.67 2.66 2.64 2.64 2.63 2.62 2.61 2.59
4.32 4.30
whw-1-22
69.42
9.5
77.56 77.24 76.92 75.34
10.0
131.79 130.76 128.84 128.77 128.29 128.00 127.76 127.45 126.83 126.67 126.57
7.46 7.45 7.40 7.40 7.38 7.38 7.35 7.35 7.33 7.33 7.32 7.32 7.32 7.31 7.30 7.29 7.28 7.26 7.26 7.26 7.25 7.24 7.24 7.23 7.23 7.22 7.22 7.21 7.20 6.58 6.54 6.41 6.39 6.37 6.35
N
7g
(E)-N,N-Diethyl-1,3-diphenylprop-2-en-1-amine (7g):
2.0
40
1.5
30
1000
900
800
700
600
500
400
300
200
100
0
1.0 0.5
20
0.0
10
-0.5
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
0
-500
0
HN
7h
0.00
1.60
3.30 3.29 3.27 3.25 3.23 3.21 3.20
4.41 4.40
6.33 6.31 6.29
7.41 7.40 7.37 7.36 7.35 7.33 7.30 7.28 7.26 7.24 7.22 7.20 7.19 6.59 6.55
whw0606-1
5.97 5.96 5.95 5.93 5.92 5.91 5.89 5.21 5.16 5.13 5.10
(E)-N-Allyl-1,3-diphenylprop-2-en-1-amine (7h):
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20
4.5
1.96
4.0 3.5 f1 (ppm)
-20 3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
50.23
5.0
64.95
5.5
77.57 77.26 76.94
6.0
1.12
1.63
0.98
0.96
143.00
whw0606-1-13c
6.5
116.30
7.0
132.66 130.61 128.85 128.73 127.68 127.54 126.64
7.5
136.90
8.0
1.00
8.19
0
16000 15000 14000 13000 12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 -1000 -2000
170
160
150
140
130
120
110
100 f1 (ppm)
90
S9
80
70
60
50
40
30
7.5
7.0
6.5
6.0
5.5
5.0
4.5
3.5
4.0 3.5 f1 (ppm)
S10 3.0
3.0
2.5 2.05
0.87
2.00
1.70
3.03 0.90
1.52 1.27 1.89
2.5 2.0 1.5
2.0
1.5
1.0
1.0
0.5
0.5 0.02
4.5 4.0 f1 (ppm)
2.32
5.0
1.02
5.5
2.96
6.0
1.99 1.98 1.98 1.98 1.97 1.97 1.96 1.96 1.96 1.95 1.95 1.95 1.93 1.92 1.90 1.58 1.57 1.56 1.55 1.54 1.54 1.53 1.51 1.49 1.48 1.47 1.45 1.44 1.28
6.5
1.05
whw0609-1
7.0
1.96
7.5
3.77 3.73 3.58 3.54 3.37 3.37 3.36 3.36 3.35 3.34
8.0
2.00
8.5
5.85 5.84 5.84 5.83 5.82 5.82 5.77 5.74
9.0 2.02 2.02 2.01 2.00 2.00 1.99 1.98 1.94 1.92 1.91 1.89 1.88 1.87 1.80 1.79 1.78 1.78 1.76 1.76 1.75 1.74 1.73 1.57 1.56 1.55 1.54 1.53 1.52 1.52 1.51 1.51 1.49 1.49 1.26
3.24 3.24 3.23 3.22 3.22
3.89 3.86 3.84 3.81
5.80 5.78 5.77 5.76 5.75 5.74 5.72
7.37 7.36 7.35 7.34 7.33 7.32 7.32 7.30 7.26 7.26 7.25 7.24 7.22
whw1115-4
0.91 0.87
3.32 2.67 1.80
7.42 7.40 7.32 7.32 7.30 7.30 7.29 7.28 7.26 7.23 7.22 7.22 7.21 7.20
NHBn
N-benzylcyclohex-2-enamine (7i)： 750
700
650
600
550
500
450
400
350
300
250
200
150
100
50
0
0.0 -0.5 -50
NBn2
N,N-dibenzylcyclohex-2-enamine (7j)：
0.0 300
280
260
240
220
200
180
160
140
120
100
80
60
40
20
0
-20
31P
1b / Pd salt
NMR 2600
whw0130-1-2-31p
2400 2200 2000 1800 1600 1400 1200 1000
1/2
800
(P,N)-chelated comlex
600 400 200 0 -200 -400 -600
55
50
45
40
35
30
25
20
15 f1 (ppm)
10
5
0
-5
-10
-15
-20
-25
whw0130-1-1.5-31p 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400
1.5/ 2
(P,N)-chelated comlex
(P,P)-chelated comlex
1200 1000 800 600 400 200 0 -200 -400 -600 -800
55
50
45
40
35
30
25
20
S11
15 f1 (ppm)
10
5
0
-5
-10
-15
-20
-25
2. HPLC spectra: NHBn
No. 1 2 ee value
Retention Time 20.189 25.104
Area % 1.560 98.440 97%
Figure 1. Enantioselective product of 1,3-diphenyl-2-propenyl acetate with benzylamine using 8b as chiral ligand in Et2O at 25 oC (Table 5, entry 6).
N
No. 1 2 ee value
Retention Time 18.535 19.376
Area % 2.968 97.032 94%
Figure 2. Enantioselective product of 1,3-diphenyl-2-propenyl acetate methylcyclohexanamine using 8b as chiral ligand in Et2O at 25 oC(Table 6, entry 6).
S12
with
N-
N
No. 1 2 ee value
Retention Time 27.149 28.678
Area % 2.857 97.143 94%
Figure 3. Enantioselective product of 1,3-diphenyl-2-propenyl acetate with diethylamine using 8b as chiral ligand in Et2O at 25 oC(Table 6, entry 7).
HN
No. 1 2 ee value
Retention Time 23.247 26.346
Area % 0.941 99.059 98%
Figure 4. Enantioselective product of 1,3-diphenyl-2-propenyl acetate with prop-2-en-1-amine using 8b as chiral ligand in Et2O at 25 oC(Table 6, entry 3).
S13
HN
No. 1 2 ee value
Retention Time 20.683 23.200
Area % 1.983 98.017 96%
Figure 5. Enantioselective product of 1,3-diphenyl-2-propenyl acetate with cyclohexanamine using 3b as chiral ligand in PhCH3 at 25 oC(Table 3, entry 1).
N
No. 1 2 ee value
Retention Time 7.917 8.292
Area % 96.060 3.940 92%
Figure 6. Enantioselective product of 1,3-diphenyl-2-propenyl acetate with pyrrolidine using 3b as chiral ligand in PhCH3 at 25 oC(Table 3, entry 3).
S14
O N
No. 1 2 ee value
Retention Time 24.000 32.775
Area % 4.390 95.610 91%
Figure 7. Enantioselective product of 1,3-diphenyl-2-propenyl acetate with morpholine using 3b as chiral ligand in PhCH3 at 25 oC(Table 3, entry 5). NHBn
No. 1 2 ee value
Retention Time 13.125 13.525
Area % 4.068 95.932 92%
Figure 8. Enantioselective product of cyclohexen-1-yl acetatea with benzylamine using 3b as chiral ligand in PhCH3 at 25 oC(Table 4, entry 1). NHBn2
S15
No. 1 2 ee value
Retention Time 13.875 14.725
Area % 5.189 94.811 90%
Figure 9. Enantioselective product of cyclohexen-1-yl acetatea with dibenzylamine using 3b as chiral ligand in PhCH3 at 25 oC (Table 4, entry 3).
S16
