Silver-Catalyzed Decarboxylative C—H Alkylation of Cyclic Aldimines with Monoalkyl Oxalates

doi:10.6023/cjoc202510026

Abstract

Silver-catalyzed decarboxylative C(sp²)—H alkylation of cyclic aldimines with monoalkyl oxalates via C—O bond cleavage has been realized under mild reaction conditions. The corresponding products were generated in moderate to good yields (30%~80%) with wide substrate scope. In addition, the late-stage modification of tyrosine- and estrone-derived cyclic aldimines was investigated, and this catalytic system was further extended to five- and seven-membered cyclic aldimines. The reactions proceeded smoothly, affording the corresponding products in moderate yields. The mechanistic studies show that the reaction undergoes a radical pathway.

Key words: silver catalysis, C—H alkylation, cyclic aldimine, monoalkyl oxalate, C—O bond cleavage

Cite this article

Jingjing Wang, Zihan Yu, Kaihua Yue, Maocong Yi, Andong Zhang, Tonghui Ding, Cuijie Wang, Mingyue Cui, Kechao Liao, Feng Li. Silver-Catalyzed Decarboxylative C—H Alkylation of Cyclic Aldimines with Monoalkyl Oxalates[J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 2096-2103.

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Entry	Catalyst	Additive	Solvent (V∶V=1∶1)	T/℃	Yield^b/%
1	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	25	Trace
2	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	45	56
3	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	60	72
4	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	80	70
5	AgOAc	K₂S₂O₈	CH₃CN/H₂O	60	67
6	AgF	K₂S₂O₈	CH₃CN/H₂O	60	64
7	AgNO₃	Na₂S₂O₈	CH₃CN/H₂O	60	69
8	AgNO₃	(NH₄)₂S₂O₈	CH₃CN/H₂O	60	63
9	AgNO₃	K₂S₂O₈	Acetone/H₂O	60	36
10	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	58
11^c	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	61
12	AgNO₃	—	CH₃CN/H₂O	60	Trace
13	—	K₂S₂O₈	CH₃CN/H₂O	60	n.d.

Entry	Catalyst	Additive	Solvent (V∶V=1∶1)	T/℃	Yield^b/%
1	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	25	Trace
2	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	45	56
3	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	60	72
4	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	80	70
5	AgOAc	K₂S₂O₈	CH₃CN/H₂O	60	67
6	AgF	K₂S₂O₈	CH₃CN/H₂O	60	64
7	AgNO₃	Na₂S₂O₈	CH₃CN/H₂O	60	69
8	AgNO₃	(NH₄)₂S₂O₈	CH₃CN/H₂O	60	63
9	AgNO₃	K₂S₂O₈	Acetone/H₂O	60	36
10	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	58
11^c	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	61
12	AgNO₃	—	CH₃CN/H₂O	60	Trace
13	—	K₂S₂O₈	CH₃CN/H₂O	60	n.d.

银催化环状醛亚胺与草酸单烷基酯的脱羧C—H烷基化反应研究