钌催化的重氮-β-酮苯甲酰胺的分子内环化反应用于合成 3-亚烷基氧化吲哚。

Ruthenium-catalyzed intramolecular cyclization of diazo-β-ketoanilides for the synthesis of 3-alkylideneoxindoles.

机构信息

State Key Laboratory for Chirosciences, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong.

出版信息

Org Biomol Chem. 2012 May 14;10(18):3749-55. doi: 10.1039/c2ob06985g. Epub 2012 Mar 28.

DOI:10.1039/c2ob06985g

PMID:22456479

Abstract

With Ru(p-cymene)Cl(2) as catalyst, diazo-β-ketoanilides would undergo intramolecular carbenoid arene C-H bond functionalization to afford 3-alkylideneoxindoles in up to 92% yields. The reaction occurs under mild conditions and exhibits excellent chemoselectivity. The lack of primary KIE (k(H)/k(D) ~ 1) suggests that the reaction should not proceed by rate-limiting C-H bond cleavage; a mechanism involving cyclopropanation of the arene is proposed.

摘要

以Ru(p-cymene)Cl2为催化剂，重氮-β-酮苯胺进行分子内碳烯芳环 C-H 键功能化反应，以高达 92%的收率得到 3-亚烷基氧化吲哚。该反应在温和条件下进行，具有优异的化学选择性。初级 KIE（k(H)/k(D)~1）的缺乏表明反应不应通过限速 C-H 键断裂进行；提出了一种涉及芳环的环丙烷化反应的机理。