Redox-Neutral Photocatalytic Cyclopropanation Via Radical/Polar Crossover

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2018 Jun 20

PMID 29916711

Citations 44

Authors

James P Phelan

Simon B Lang

Jordan S Compton

Christopher B Kelly

Ryan Dykstra

Osvaldo Gutierrez

Gary A Molander

Affiliations

Soon will be listed here.

Abstract

A benchtop stable, bifunctional reagent for the redox-neutral cyclopropanation of olefins has been developed. Triethylammonium bis(catecholato)iodomethylsilicate can be readily prepared on multigram scale. Using this reagent in combination with an organic photocatalyst and visible light, cyclopropanation of an array of olefins, including trifluoromethyl- and pinacolatoboryl-substituted alkenes, can be accomplished in a matter of hours. The reaction is highly tolerant of traditionally reactive functional groups (carboxylic acids, basic heterocycles, alkyl halides, etc.) and permits the chemoselective cyclopropanation of polyolefinated compounds. Mechanistic interrogation revealed that the reaction proceeds via a rapid anionic 3- exo- tet ring closure, a pathway consistent with experimental and computational data.

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