Table 1 Optimization of coupling of ketimine 1a and allyl phenyl ether 2aa,b.

From: Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

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Entry

Base (equiv.)

Solvent

Conc.

Assay yield (%)

1

NaN(SiMe3)2 (3.0)

MTBE

0.2 M

64

2

NaN(SiMe3)2 (3.0)

DME

0.2 M

10

3

NaN(SiMe3)2 (3.0)

CPME

0.2 M

74

4

NaN(SiMe3)2 (3.0)

THF

0.2 M

20

5

NaN(SiMe3)2 (3.0)

Dioxane

0.2 M

0

6

NaN(SiMe3)2 (3.0)

DMSO

0.2 M

0

7

NaN(SiMe3)2 (3.0)

DMF

0.2 M

0

8

NaN(SiMe3)2 (3.0)

Toluene

0.2 M

84

9

LiOtBu (3.0)

Toluene

0.2 M

0

10

NaOtBu (3.0)

Toluene

0.2 M

0

11

KOtBu (3.0)

Toluene

0.2 M

0

12

LiN(SiMe3)2 (3.0)

Toluene

0.2 M

23

13

KN(SiMe3)2 (3.0)

Toluene

0.2 M

8

14

NaN(SiMe3)2 (2.0)

Toluene

0.2 M

74

15

NaN(SiMe3)2 (4.0)

Toluene

0.2 M

89 (86)c

16d

NaN(SiMe3)2 (4.0)

Toluene

0.2 M

73

17e

NaN(SiMe3)2 (4.0)

Toluene

0.2 M

70

18

NaN(SiMe3)2 (4.0)

Toluene

0.1 M

63

  1. aReaction conditions: 1a (0.2 mmol, 2.0 equiv.), 2a (0.1 mmol, 1.0 equiv.), room temperature, 12 h.
  2. bAssay yields determined by 1H NMR spectroscopy of the crude reaction mixtures using CH2Br2 as an internal standard.
  3. cIsolated yield.
  4. d1a (1.5 equiv.).
  5. e6 h.
  6. MTBE methyl tert-butyl ether, DME dimethoxyethane, CPME cyclopentyl methyl ether, THF tetrahydrofuran, DMSO dimethyl sulfoxide, DMF N,N-dimethylformamide.
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