Table 1 Selected optimizationa.

From: Enyne diketones as substrate in asymmetric Nazarov cyclization for construction of chiral allene cyclopentenones

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entry

diazo

variation from conditions A

4 (yield, %)b

1

1a

none

79

2

1b

none

68

3

1c

none

55

4

1d

none

64

5

1e

none

25

6

1 f

none

52

7

1a

toluene instead of hexane

54

8

1a

CH2Cl2 instead of hexane

31

9

1a

Rh2(esp)4 instead of Rh2(OAc)4

65

10

1a

Rh2(TFA)4 instead of Rh2(OAc)4

63

11

1a

SiO2 instead of MgO, 24 h

43

  1. aMethod A: 1 (0.3 mmol, 1.5 eq.), 2a (0.2 mmol, 1eq.) and Rh2(OAc)4 (2 mol%) in hexane (2 mL) stirred at rt. for 12 h under N2. Then, to the solution were added MgO (200 mg, 50 eq.), CH2Cl2 (5 mL) and stirred at 40 oC for another 3 h. bIsolated yield, dr > 19:1 (determined by 1H NMR analysis).