Table 1 Optimization of the reaction conditions for the fluoro-carbonylation of 1 and 2.

From: Pd-catalyzed fluoro-carbonylation of aryl, vinyl, and heteroaryl iodides using 2-(difluoromethoxy)-5-nitropyridine

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Entry

Pd (mol%)

Ligand (mol%)

CsF (equiv)

Yielda

1

Pd(OAc)2 (10)

PPh3 (10)

2.0

73

2

–

PPh3 (10)

2.0

0

3

Pd(OAc)2 (10)

–

2.0

18

4

Pd(OAc)2 (10)

PPh3 (20)

2.0

77

5

Pd(OAc)2 (10)

PPh3 (30)

2.0

84

6

Pd(OAc)2 (10)

PPh3 (40)

2.0

77

7

Pd(TFA)2 (10)

PPh3 (30)

2.0

95

8

Pd(TFA)2 (10)

TFP (30)

2.0

83

9

Pd(TFA)2 (10)

PCy3 (30)

2.0

43

10

Pd(TFA)2 (10)

P(o-Tol)3 (30)

2.0

40

11

Pd(TFA)2 (10)

Xphos (30)

2.0

49

12

Pd(TFA)2 (10)

DPPE (15)

2.0

74

13

Pd(TFA)2 (10)

BINAP (15)

2.0

84

14

Pd(TFA)2 (10)

DPEphos (15)

2.0

86

15

Pd(TFA)2 (10)

Xantphos (15)

2.0

>99 (92)

16b

Pd(TFA)2 (1)

Xantphos (1.5)

1.5

>99 (92)

  1. Conditions: 1a (0.1 mmol), 2 (0.2 mmol 2.0 equiv), CsF (0.2 mmol, 2.0 equiv), Pd, and ligand were stirred for 15 h at 70 °C in anhydrous DMF (1.5 mL).
  2. aDetermined by 19F NMR spectroscopy. The numbers in parentheses refer to the isolated yield.
  3. b1a (0.3 mmol), 2 (0.36 mmol, 1.2 equiv), CsF (0.45 mmol, 1.5 equiv), Pd(TFA)2 (1.0 mol%), and Xantphos (1.5 mol%) were stirred for 15 h at 70 °C in anhydrous DMF (2.0 mL).
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