Prev. Article Next Article Table of Contents

Communication

Gold(I)-Catalyzed Ring Expansion of Cyclopropanols and Cyclobutanols

Supporting Info

Jordan P. Markham, Steven T. Staben, and F. Dean Toste*

Department of Chemistry, University of California, Berkeley, California 94720

J. Am. Chem. Soc., 2005, 127 (27), pp 9708–9709

DOI: 10.1021/ja052831g

Publication Date (Web): June 15, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, fdtoste@berkeley.edu

Abstract

The rearrangement of 1-alkynyl cyclobutanols and cyclopropanols to alkylidene cycloalkanones catalyzed by cationic triarylphosphine gold(I) complexes is described. The reaction tolerates terminal alkynes as well as alkyl, aryl, and halo-substitution at the acetylenic position and stereoselectively provides a single olefin isomer. The gold(I)-catalyzed rearrangement is stereospecific with regard to substituents on the ring, thus providing a practical method for the stereoselective synthesis of highly substituted cyclopentanones from cyclopropanols. The reaction stereoselectively provides a single olefin isomer and is stereospecific with regard to substituents on the ring via sequential gold(I)-catalyzed ring expansion reactions.

View: Full Text HTML | Hi-Res PDF