Synthesis of 4-Alkyl-4-alkoxybutenolides Having Unsaturated Side Chains via Chromium Carbene Complex Photochemistry: (+)-Cerulenin

Tracey E. Kedar; Michael W. Miller; Louis S. Hegedus

doi:10.1021/jo960664k

Synthesis of 4-Alkyl-4-alkoxybutenolides Having Unsaturated Side Chains via Chromium Carbene Complex Photochemistry: (+)-Cerulenin

J Org Chem. 1996 Sep 6;61(18):6121-6126. doi: 10.1021/jo960664k.

Authors

Tracey E. Kedar¹, Michael W. Miller, Louis S. Hegedus

Affiliation

¹ Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523.

PMID: 11667445
DOI: 10.1021/jo960664k

Abstract

The photochemical reaction between optically active ene carbamates and chromium alkoxycarbene complexes containing unsaturated aliphatic side chains was further developed. Although remote olefinic groups, including conjugated dienes, were tolerated, a homoallylic side chain underwent intramolecular reaction to give a strained cyclobutanone. (+)-Cerulenin was synthesized utilizing the photochemical reaction of an alkynylcarbene complex with an optically active ene carbamate and the bis(pi-crotyl)nickel halide alkylation of a vinyl bromide as key steps.