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银催化炔酸酯和二烷基膦酸酯的自由基环化反应合成 3-膦酰基香豆素。

Silver-catalyzed synthesis of 3-phosphorated coumarins via radical cyclization of alkynoates and dialkyl H-phosphonates.

机构信息

College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University , Zhengzhou 450052, P. R. China.

出版信息

Org Lett. 2014 Jun 20;16(12):3356-9. doi: 10.1021/ol5013839. Epub 2014 Jun 12.

DOI:10.1021/ol5013839
PMID:24921182
Abstract

Ag2CO3-catalyzed difunctionalization of alkynes via a radical phosphonation and C-H functionalization tandem process was developed to synthesize various 3-phosphonated coumarins in moderate to high yields with high regioselectivity. A catalytic amount of cheap and nontoxic silver salt was employed in the domino C-P and C-C formation of alkynoates for the first time. Mechanistic studies indicate that the reaction pathway might proceed via the generation and cyclization of a phosphonated vinyl radical intermediate.

摘要

Ag2CO3 催化炔烃的双官能团化通过自由基膦化和 C-H 官能化串联反应得到开发,以中等至高产率和高区域选择性合成各种 3-膦化香豆素。首次在炔酸酯的串联 C-P 和 C-C 形成中使用了催化量的廉价且无毒的银盐。机理研究表明,反应途径可能是通过膦化乙烯基自由基中间体的生成和环化来进行的。

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