Table 1 Optimization of reaction conditionsa View full size image

From: Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization

entry

[Co]

solvent

additive

yield (%)b

dr (cis-3aa/trans-3aa)c

ee of cis-3aa (%)c

1

Co-1

TFE

CsOAc

95

10:90

2

Co-2

TFE

CsOAc

67

43:57

3

Co-3

TFE

CsOAc

94

18:82

4d

(Ra)-Co-4

TFE

CsOAc

10

80:20

69

5

(Ra)-Co-5

TFE

CsOAc

12

90:10

>99

6

(Ra)-Co-6

TFE

CsOAc

19

93:7

>99

7

(Ra)-Co-7

TFE

CsOAc

25

95:5

>99

8

(Ra)-Co-7

TFE

CsOPiv

39

96:4

>99

9

(Ra)-Co-7

TFE

NaOPiv

60

96:4

>99

10

(Ra)-Co-7

TFE

HOPiv

59

92:8

>99

11

(Ra)-Co-7

HFIP

NaOPiv

98

93:7

98

12

(Ra)-Co-7

TFE/HFIP (v/v = 1:1)

NaOPiv

98

94:6

99

13

(Ra)-Co-7

TFE/HFIP (v/v = 3:1)e

NaOPiv

98

95:5

>99

14

(Ra)-Rh-1

TFE/HFIP (v/v = 3:1)e

NaOPiv

ND

  1. aReaction conditions: 1a (0.05 mmol), 2a (0.075 mmol), [Co] (5 mol%), additive (30 mol%) in solvent (0.3 mL) at 50 °C for 18 h.
  2. bCombined yield of cis-3aa and trans-3aa.
  3. cThe ratio of cis-3aa/trans-3aa and the ee value of cis-3aa were determined by HPLC with a chiral stationary phase.
  4. dAt 80 °C for 10 h.
  5. eTFE (0.3 mL) and HFIP (0.1 mL) were used as the solvent. ND = not detected.