Table 1 Optimization of reaction conditionsa

From: Catalytic aromatic C−H borylation via strained Si and Ge metallacycles

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Entry

[B]

Cat [M] (mol%)

L (mol%)

Base

Solvent

Yield (%)b

1

HBpin

[Ir(cod)OMe]2 (2.5)

L1 (5.0)

–

THF

<5

2

HBpin

[Ir(cod)OMe]2 (2.5)

L1 (5.0)

LiOAc

THF

8

3

HBpin

[Ir(cod)OMe]2 (2.5)

L1 (5.0)

NaOAc

THF

19

4

HBpin

[Ir(cod)OMe]2 (2.5)

L1 (5.0)

KOAc

THF

26

5

HBpin

[Ir(cod)OMe]2 (2.5)

L1 (5.0)

K2CO3

THF

<5

6

HBpin

[Ir(cod)OMe]2 (2.5)

L2 (5.0)

KOAc

THF

33

7

HBpin

[Ir(cod)OMe]2 (2.5)

L3 (5.0)

KOAc

THF

58

8

HBpin

[Ir(cod)OMe]2 (2.5)

L4 (5.0)

KOAc

THF

75 (74)c

9

HBpin

[Ir(cod)OMe]2 (2.5)

L5 (5.0)

KOAc

THF

59

10

HBpin

[Ir(cod)OMe]2 (2.5)

L4 (5.0)

KOAc

1,4-dioxane

32

11

HBpin

[Ir(cod)OMe]2 (2.5)

L4 (5.0)

KOAc

Toluene

14

12

HBpin

[Ir(cod)OMe]2 (2.5)

L4 (5.0)

KOAc

DMF

0

13

B2pin2

[Ir(cod)OMe]2 (2.5)

L4 (5.0)

KOAc

THF

39

14

HBpin

[Ir(cod)Cl]2 (2.5)

L4 (5.0)

KOAc

THF

56

15

HBpin

[Ir(cod)acac] (5.0)

L4 (5.0)

KOAc

THF

31

16

HBpin

[Rh(cod)Cl]2 (2.5)

L4 (5.0)

KOAc

THF

0

17

HBpin

[Ir(cod)OMe]2 (1.0)

L4 (2.0)

KOAc

THF

44

18

HBpin

–

L4 (5.0)

KOAc

THF

0

  1. aReaction conditions: cat [M] (1.0–5.0 mol%), L (2.0–5.0 mol%), 1a (0.5 mmol), boron source (1.25 mmol), and base (1.25 mmol) in 1.5 mL of solvent at 125 °C for 6 h under argon.
  2. bYield was determined by GCMS.
  3. cIsolated yield.
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