无配体参与的铱催化的苄位二级碳氢键的硼化反应

doi:10.6023/cjoc202101009

摘要/Abstract

报道了无外加配体参与的以吡唑作为导向基团的铱催化的sp³碳氢键的区域选择性硼化反应. 在催化量的[Ir(OMe)(cod)]₂存在下, 该反应能够顺利地将苄位的二级碳氢键转化成碳硼键. 该反应具有非常广谱的官能团兼容性, 能够以良好到优秀的产率生成相应的产物. 此外, 导向基团吡唑能够通过臭氧接转化成酰胺.

关键词: 碳氢键活化, 铱, 合成方法, 硼化

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

引用此文

刘路华, 杜荣荣, 徐森苗. 无配体参与的铱催化的苄位二级碳氢键的硼化反应[J]. 有机化学, 2021, 41(4): 1572-1581.

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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参考文献 24

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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