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Published on: August 16, 2018
Nickel-Catalyzed Ring-Opening Allylation of Cyclopropanols via Homoenolate
Yoshiya Sekiguchi1, Yan Ying Lee1, Naohiko Yoshikai1,2
1Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Abstract:
We report herein a nickel-catalyzed ring-opening allylation of cyclopropanols with allylic carbonates that occurs under mild and neutral conditions. The reaction displays linear selectivity for both linear and branched acyclic allylic carbonates and is also applicable to cyclic allylic carbonates, affording a variety of δ,ε-unsaturated ketones in moderate to good yields. Mechanistic experiments are in accord with a catalytic cycle involving decarboxylative oxidative addition of allylic carbonate to Ni(0), alkoxide exchange with cyclopropanol, cyclopropoxide-to-homoenolate conversion on Ni(II), and C-C reductive elimination.
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