Table 1 The condition screening for the difluorocarbene-induced tertiary amine-involved Stevens rearrangement

From: Difluorocarbene-induced [1,2]- and [2,3]-Stevens rearrangement of tertiary amines

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Solvent

Base (X equiv.)

[:CF2] (3 equiv.)

Yield (%)a

1

CH3CN

K2CO3 (3)

BrCF2COOK (2a)

45b

2

CH3CN

K2CO3 (3)

BrCF2COONa (2b)

35

3

CH3CN

K2CO3 (3)

BrCF2COOEt (2c)

25

4

CH3CN

K2CO3 (3)

ClCF2COONa (2d)

51

5

CH3CN

K2CO3 (3)

ClCF2H (2e)

trace

6

CH3CN

HCOONa (3)

ClCF2COONa (2d)

trace

7

CH3CN

Rb2CO3 (3)

ClCF2COONa (2d)

64

8

CH3CN

LiOH (3)

ClCF2COONa (2d)

trace

9

CH3CN

Na2CO3 (3)

ClCF2COONa (2d)

31

10

CH3CN

Et3N (3)

ClCF2COONa (2d)

ND

11

CH3CN

K3PO4 (3)

ClCF2COONa (2d)

85b

12

CH3CN

K3PO4 (3)

2d (1 equiv.)

71

13

CH3CN

K3PO4 (3)

2d (1.5 equiv.)

86

14

CH3CN

K3PO4 (1.5)

2d (1.5 equiv.)

55

15

CH3CN

K3PO4 (2)

2d (1.5 equiv.)

71

16

CH3CN

K3PO4 (2.5)

2d (1.5 equiv.)

78

  1. Reaction condition: a1 (1 equiv., 0.2 mmol), 2 (3 equiv., 0.6 mmol), base (3 equiv.), CH3CN (2 mL) at 90 °C for 12 h under argon; GC yields; bisolated yields; cND not detected.
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