Pd-Catalyzed Asymmetric Allylic Amination Using

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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.

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

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