Merging Electron Transfer Activation with 1,2-Metalate Migration: Deoxygenative Silylation of Amides

doi:10.6023/cjoc202212019

Abstract

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

Cite this article

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

电子转移活化和1,2-硼迁移相结合实现酰胺脱氧硅基化