Mechanistic Study of Nickel-catalyzed Ynal Reductive Cyclizations Through Kinetic Analysis

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2011 Mar 29

PMID 21438642

Citations 9

Authors

Ryan D Baxter

John Montgomery

Affiliations

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Abstract

The mechanism of nickel-catalyzed, silane-mediated reductive cyclization of ynals has been evaluated. The cyclizations are first-order in [Ni] and [ynal] and zeroth-order in [silane]. These results, in combination with the lack of rapid silane consumption upon reaction initiation, are inconsistent with mechanisms involving reaction initiation by oxidative addition of Ni(0) to the silane. Silane consumption occurs only when both the alkyne and aldehyde are present. Mechanisms involving rate-determining oxidative cyclization to a metallacycle followed by rapid reaction with the silane are consistent with the data obtained.

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