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Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

Published on: September 18, 2016

Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage

Junfeng Yang^1,2, Yuto Mori³, Masahiro Yamanaka³

¹Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, 637371, Singapore.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|April 16, 2020

Abstract:

A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C-H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C-C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations.

Keywords:

C−C bond cleavage C−H activation cobalt cyclopropanes hydroacylation

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