Table 1 Reaction optimization

From: Palladium-catalyzed asymmetric migratory diarylation of unactivated directing-group-free internal alkenes

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Entry

Solvents

Ligands

Additives

[Pd] sources

Yield of 4a (%)

Ee of 4a (%)

1

DME

L1

A1

Pd(OAc)2

48

88

2

1,4-Dioxane

L1

A1

Pd(OAc)2

48

92

3

DME/1,4-Dioxane (v/v = 3/1)

L1

A1

Pd(OAc)2

67

84

4

DME/1,4-Dioxane (v/v = 1/1)

L1

A1

Pd(OAc)2

56

84

5

DME/1,4-Dioxane (v/v = 1/3)

L1

A1

Pd(OAc)2

57

92

6

DME/1,4-Dioxane (v/v = 1/3)

L2

A1

Pd(OAc)2

55

88

7

DME/1,4-Dioxane (v/v = 1/3)

L3

A1

Pd(OAc)2

62

93

8

DME/1,4-Dioxane (v/v = 1/3)

L4

A1

Pd(OAc)2

53

88

9

DME/1,4-Dioxane (v/v = 1/3)

L5

A1

Pd(OAc)2

56

87

10

DME/1,4-Dioxane (v/v = 1/3)

L6

A1

Pd(OAc)2

52

90

11

DME/1,4-Dioxane (v/v = 1/3)

L3

A2

Pd(OAc)2

63

93

12

DME/1,4-Dioxane (v/v = 1/3)

L3

A3

Pd(OAc)2

62

93

13

DME/1,4-Dioxane (v/v = 1/3)

L3

A4

Pd(OAc)2

54

93

14

DME/1,4-Dioxane (v/v = 1/3)

L3

A5

Pd(OAc)2

65

93

15

DME/1,4-Dioxane (v/v = 1/3)

L3

A6

Pd(OAc)2

57

91

16b

DME/1,4-Dioxane (v/v = 1/3)

L3

A5

[Pd(allylCl)]2

79(79)a

93

17

DME/1,4-Dioxane (v/v = 1/3)

L3

A5

Pd(dba)2

69

93

18b

DME/1,4-Dioxane (v/v = 1/3)

L3

A5

[Pd(π-cinnamyl)Cl]2

72

93

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  1. Reaction conditions: alkene 1a (1.0 equiv, 0.10 mmol), aryl diazonium salt 2a (2.0 equiv, 0.20 mmol), arylboronic acid 3a (3.0 equiv, 0.30 mmol), [Pd] (5.0 mol %, 0.005 mmol), chiral ligand (10 mol %, 0.01 mmol), additive (16 mol %, 0.016 mmol), and Ag2CO3 (1.0 equiv, 0.10 mmol) in solvents (0.2 mL, 0.5 M) at 25 °C. The yields were determined by 1H NMR using dibromomethane as an internal standard, and the ee values were determined by chiral HPLC. aIsolated yields within the parentheses. b2.5 mol % [Pd] was used.
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