Table 1 Optimization of reaction conditionsa.

From: Enantioselective cyanation via radical-mediated C–C single bond cleavage for synthesis of chiral dinitriles

View full size image

entry

[Cu]/mol%

ligand

Solvent

T/oC

Yield (ee)/%

1b,c

10

L1

DCM

RT

23 (91)

2b,c

10

L1

DCM

50

63 (88)

3c,d

5

L1

DCM

50

55 (90)

4c,e

15

L1

DCM

50

58 (88)

5

2

L1

DCM

RT

71 (91)

6

2

L1

CH3CN

RT

70 (91)

7

2

L1

Acetone

RT

24 (93)

8

2

L1

Benzene

RT

81 (87)

9

2

L1

PhCl

RT

80 (87)

10

2

L1

DMF

RT

73 (91)

11

2

L1

DMAc

RT

73 (92)

12

2

L2

DMAc

RT

68 (88)

13

2

L3

DMAc

RT

70 (86)

14

2

L4

DMAc

RT

58 (75)

15

2

L5

DMAc

RT

40 (73)

16

2

L6

DMAc

RT

56 (-43)

17f

2

L1

DMAc

RT

78 (92)

18g

2

L1

DMAc

RT

12 (90)

19h

2

L1

DMAc

RT

9 (91)

20i

0

L1

DMAc

RT

14 (0)

  1. Ir(ppy)3  Tris(2-phenylpyridine)iridium, DCM  Dichloromethane, DMF  N,N-Dimethylformamide, DMAc  N,N-Dimethylacetamide, RT  room temperature
  2. aReaction conditions: 1a (0.10 mmol), TMSCN (3 equiv), Cu(MeCN)4PF6 (2 mol%), ligand (3 mol%), Ir(ppy)3 (0.5 mol%) in solvent (1.0 mL) at RT for 36 h under the irradiation of 5 W blue LEDs
  3. bCu(MeCN)4PF6 (10 mol%), L1 (12 mol%)
  4. c24 h
  5. dCu(MeCN)4PF6 (5 mol%), L1 (6 mol%)
  6. eCu(MeCN)4PF6 (15 mol%), L1 (18 mol%)
  7. fTMSCN (1.5 equiv)
  8. gIn dark
  9. hNo Ir(ppy)3
  10. iNo Cu(MeCN)4PF6
Back to article page