Ruthenium-catalyzed Cascade C-H Activation/annulation of -alkoxybenzamides: Reaction Development and Mechanistic Insight

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Jun 7

PMID 34094402

Citations 2

Authors

Liangliang Song

Xiaoyong Zhang

Xiao Tang

Luc Van Meervelt

Johan Van der Eycken

Jeremy N Harvey

Erik V Van der Eycken

Affiliations

Soon will be listed here.

Abstract

A highly selective ruthenium-catalyzed C-H activation/annulation of alkyne-tethered -alkoxybenzamides has been developed. In this reaction, diverse products from inverse annulation can be obtained in moderate to good yields with high functional group compatibility. Insightful experimental and theoretical studies indicate that the reaction to the inverse annulation follows the Ru(ii)-Ru(iv)-Ru(ii) pathway involving N-O bond cleavage prior to alkyne insertion. This is highly different compared to the conventional mechanism of transition metal-catalyzed C-H activation/annulation with alkynes, involving alkyne insertion prior to N-O bond cleavage. this pathway, the generated acetic acid from the N-H/C-H activation step facilitates the N-O bond cleavage to give the Ru-nitrene species. Besides the conventional mechanism forming the products standard annulation, an alternative and novel Ru(ii)-Ru(iv)-Ru(ii) mechanism featuring N-O cleavage preceding alkyne insertion has been proposed, affording a new understanding of transition metal-catalyzed C-H activation/annulation.

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