Ligand-Free Iridium-Catalyzed Borylation of Secondary Benzylic C—H Bonds

doi:10.6023/cjoc202101009

Abstract

The ligand-free regioselective iridium-catalyzed C(sp³)—H bond borylation using pyrazole as the directing group is reported. The reaction occurs smoothly at the secondary benzylic position in the presence of a catalytic amount of commercially available [Ir(OMe)(cod)]₂. A variety of functionalities could be well tolerated, affording corresponding products in good to excellent yields. The pyrazole could be degraded into amide by ozonolysis.

Key words: C—H activation, iridium, synthetic methods, borylation

Cite this article

Luhua Liu, Rongrong Du, Senmiao Xu. Ligand-Free Iridium-Catalyzed Borylation of Secondary Benzylic C—H Bonds[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1572-1581.

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Entry^a	Variation from standard conditions	Yield^b/% of 3
1	None	90
2	[IrCl(cod)]₂ instead of [IrOMe(cod)]₂	81
3	HBpin instead of B₂pin₂	Trace
4	1.0 equiv of B₂pin₂ was used	50
5	2 mol% dtbpy was used	n.d.
6	2 mol% P(C₆F₅)₃ was used	80
7	80 ℃ instead of 100 ℃	60
8	1,4-Dioxane instead of n-heptane	33
9	n-Hexane instead of n-heptane	77

Entry^a	Variation from standard conditions	Yield^b/% of 3
1	None	90
2	[IrCl(cod)]₂ instead of [IrOMe(cod)]₂	81
3	HBpin instead of B₂pin₂	Trace
4	1.0 equiv of B₂pin₂ was used	50
5	2 mol% dtbpy was used	n.d.
6	2 mol% P(C₆F₅)₃ was used	80
7	80 ℃ instead of 100 ℃	60
8	1,4-Dioxane instead of n-heptane	33
9	n-Hexane instead of n-heptane	77

无配体参与的铱催化的苄位二级碳氢键的硼化反应