Table 1 Asymmetric [3+2] coupling of 3-substituted indoles with quinone monoiminea

From: Permanent porous hydrogen-bonded frameworks with two types of Brønsted acid sites for heterogeneous asymmetric catalysis

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Entry

Cat.

R1

R2

R3

Yield (%)b

ee (%)c

1

1-Ni

Me

H

H

92

99.9 (S)

2

 

Me

Me

H

90

95 (S)

3

 

Me

H

5-Me

92

94 (S)

4

 

Me

H

6-F

90

95 (S)

5

 

Me

H

6-Me

95

99.9 (S)

6

 

Me

H

5-OMe

86

91 (S)

7

 

Me

H

5-Br

83

92 (S)

8d

 

Phenyl

H

H

65

99.7 (S)

9d

 

Benzyl

H

H

37

94 (S)

10d

 

PIMEe

H

H

9

n.d.

11

 

Me

H

H

94

99.9 (R)f

12

1-Co

Me

Me

H

92

94 (S)

13

 

Me

H

5-Me

89

93 (S)

14

 

Me

H

6-F

88

93 (S)

15

PhCO2Hg

Me

H

H

n.d.

n.d.

16

1-Ni*/Me4Lh

Me

H

H

94 (79)

89 (78) (S)

17

 

Me

H

5-Me

90 (77)

87 (78) (S)

18

 

Me

H

6-F

93 (76)

89 (75) (S)

19

 

Me

H

5-Br

91 (72)

87 (76) (S)

20

 

Phenyl

H

H

70 (73)

91 (80) (S)

21

 

Benzyl

H

H

69 (72)

90 (87) (S)

22

 

PIMEe

H

H

56 (64)

n.d. (n.d.)

  1. aReaction conditions: 3-substituted indole (0.10 mmol), quinone monoimine (0.15 mmol), and (S)-1-Ni (0.04 mol% catalyst based on indole) in CH3CN (1 mL), 0 °C, 14 h
  2. bIsolated yield
  3. cDetermined by HPLC
  4. dReaction time: 48 h
  5. ePIME = phthalimidoethyl (size: 6.5  ×  15.2  Å2, Supplementary Figure 13)
  6. fThe R enantiomer was produced using (R)-1-Ni as the catalyst
  7. gCatalyzed by 0.24 mol% of benzoic acid
  8. hCatalyzed by 0.03 mol% of the discrete cage 1-Ni* and 0.24 mol% of (S)-Me4L