Table 1 Optimization of reaction conditionsa

From: Regioselective Ni-Catalyzed reductive alkylsilylation of acrylonitrile with unactivated alkyl bromides and chlorosilanes

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Entry

Ni Cat.

Ligand

Reductant

Solvent

Yield of 4 (%)

Recovery of 1a (%)

1

NiBr2•DME

L1

Zn

DMA

0

77

2

NiBr2•DME

L2

Zn

DMA

0

87

3

NiBr2•DME

L3

Zn

DMA

6

73

4

NiBr2•DME

L4

Zn

DMA

30

52

5

NiBr2•DME

L5

Zn

DMA

0

97

6

NiBr2•DME

L6

Zn

DMA

14

79

7

Ni(acac)2

L4

Zn

DMA

15

83

8

Ni(OTf)2

L4

Zn

DMA

25

55

9

Ni(COD)2

L4

Zn

DMA

12

54

10

Ni(PPh3)2Cl2

L4

Zn

DMA

35

47

11

Ni(PPh3)2Cl2

L4

Zn

DMSO

0

70

12

Ni(PPh3)2Cl2

L4

Zn

CH3CN

0

94

13

Ni(PPh3)2Cl2

L4

Zn

EtOAc

0

88

14b

Ni(PPh3)2Cl2

L4

Zn

DMA

60

21

15b,c

Ni(PPh3)2Cl2

L4

Zn

DMA

55

63

16b

Ni(PPh3)2Cl2

L4

Mn

DMA

4

64

17b

Ni(PPh3)2Cl2

L4

TDAE

DMA

trace

72

18b,d

Ni(PPh3)2Cl2

L4

Zn

DMA

79 (73e, 55f)

0

  1. DME dimethyl ether, DMA N,N-dimethylacetamide, acac acetylacetonate, OTf triflate, COD 1,5-cyclooctadiene, DMSO dimethyl sulfoxide, EtOAc ethyl acetate, TDAE tetrakis(dimethylamino)ethylene.
  2. aReaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), 3a (0.6 mmol), Ni catalyst (10 mol%), ligand (12 mol%), reductant (0.6 mmol), solvent (1 mL), 25 °C, 24 h, N2 atmosphere.
  3. bLigand (20 mol%) was used.
  4. c1a (0.3 mmol), 2a (0.2 mmol) were used.
  5. dThe reaction run at 35 °C for 36 h.
  6. eThe isolated yield was shown in parentheses on 0.4 mmol scale.
  7. f(3-iodopropyl)benzene as the substrate.