A Stereochemical Study of the Isomerization of Cyclopropyl Ethers to Allyl Ethers Catalyzed with Zinc Iodide

Takashi Sugimura; Tohru Futagawa; Atsushi Mori; Ilhyong Ryu; Noboru Sonoda; Akira Tai

doi:10.1021/jo960448b

A Stereochemical Study of the Isomerization of Cyclopropyl Ethers to Allyl Ethers Catalyzed with Zinc Iodide

J Org Chem. 1996 Sep 6;61(18):6100-6103. doi: 10.1021/jo960448b.

Authors

Takashi Sugimura¹, Tohru Futagawa, Atsushi Mori, Ilhyong Ryu, Noboru Sonoda, Akira Tai

Affiliation

¹ Faculty of Science, Himeji Institute of Technology, Kanaji, Kamigori, Ako-gun 678-12, Japan, and Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565 Japan.

PMID: 11667441
DOI: 10.1021/jo960448b

Abstract

Optically active 1-alkoxybicyclo[4.1.0]heptane was converted using zinc iodide as a catalyst to 2-alkoxymethylidenecyclohexane without loss of optical purity. The mechanism of the isomerization was studied using a stereochemical analysis of the product and deuterium labeling experiments. The results indicated that the isomerization takes place through a stepwise mechanism that involves an attack of zinc iodide on the cyclopropane ring to cause ring opening, followed by an intramolecular 1,2-hydride shift with liberation of the zinc iodide.