电子转移活化和1,2-硼迁移相结合实现酰胺脱氧硅基化

doi:10.6023/cjoc202212019

摘要/Abstract

报道了在SmI₂/Mg存在下, 使用膦配体促进的芳基酰胺与硅硼试剂的直接脱氧硅基化反应, 以中等至优异的收率和良好的官能团兼容性, 得到一系列具有高价值的α-氨基硅烷化合物. 这一策略成功的关键在于电子转移诱导活化酰胺和1,2-硼迁移的融合, 通过添加双膦配体Xantphos能够提高反应的效率. 该反应具有操作简单和条件温和的优点, 且所需原料易得, 产物价值高.

关键词: 酰胺, 电子转移, 硅硼试剂, 1,2-硼迁移, α-氨基硅烷

A direct deoxygenative silylation of amides with silylboronate reagents is developed in the presence of SmI₂/Mg, affording a variety of high value-added α-aminosilane compounds in moderate to excellent yields with good functional group compatibility. The key to the success of this strategy lies in the merging of activation of amides induced by electron transfer with 1,2-metalate migration. The addition of Xantphos ligand can improve the reaction efficiency. The reactions are operationally simple and proceed under mild conditions, the raw materials are easily available and the products are highly valuable.

Key words: amide, electron transfer, silylboronate reagent, 1,2-metalate migration, α-aminosilane

引用此文

杨雯涵, 焦继文, 王晓明. 电子转移活化和1,2-硼迁移相结合实现酰胺脱氧硅基化[J]. 有机化学, 2023, 43(5): 1857-1867.

Wenhan Yang, Jiwen Jiao, Xiaoming Wang. Merging Electron Transfer Activation with 1,2-Metalate Migration: Deoxygenative Silylation of Amides[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1857-1867.

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Entry	Metal powder (equiv.)	SmI₂ (equiv.)	Ligand (0.1 equiv.)	Yield^b/%
1	Sm (2.0)	2.0	—	70
2	—	2.0	—	21
3	Mg (2.0)	2.0	—	81
4	Mg (2.0)	2.0	dppm	74
5	Mg (2.0)	2.0	dppp	45
6	Mg (2.0)	2.0	dppf	77
7	Mg (2.0)	2.0	Xantphos	98 (98)^c
8	Mg (2.0)	2.0	PPh₃	47
9	Mg (2.0)	2.0	L1	71
10	Mg (2.0)	2.0	L2	73
11	Mg (2.0)	2.0	BINAP	81
12	Mg (2.0)	1.0	Xantphos	67
13	Mg (2.0)	2.0	Xantphos^d	69
14	Mg (5.0)	0.2	Xantphos	34

Entry	Metal powder (equiv.)	SmI₂ (equiv.)	Ligand (0.1 equiv.)	Yield^b/%
1	Sm (2.0)	2.0	—	70
2	—	2.0	—	21
3	Mg (2.0)	2.0	—	81
4	Mg (2.0)	2.0	dppm	74
5	Mg (2.0)	2.0	dppp	45
6	Mg (2.0)	2.0	dppf	77
7	Mg (2.0)	2.0	Xantphos	98 (98)^c
8	Mg (2.0)	2.0	PPh₃	47
9	Mg (2.0)	2.0	L1	71
10	Mg (2.0)	2.0	L2	73
11	Mg (2.0)	2.0	BINAP	81
12	Mg (2.0)	1.0	Xantphos	67
13	Mg (2.0)	2.0	Xantphos^d	69
14	Mg (5.0)	0.2	Xantphos	34