Diastereoselective Synthesis of Eight-Membered-Ring Allenes from Propargylic Epoxides and Aldehydes by Silylene Insertion into Carbon–Oxygen Bonds

by Christina Z. Rotsides, Chunhua Hu, K. A. Woerpel*

Bent out of shape: Silver-catalyzed insertions of silylenes into propargylic CO bonds of epoxides regioselectively form 1,2-silaoxetanes, which add to aldehydes to give the title allenes as single diastereomers (see scheme; Ts=4-toluenesulfonyl). An X-ray crystal structure confirmed the stereochemistry of the allene, which is bent significantly from linearity (164°).

Angewandte Chemie International Edition

Article first published online: 9 OCT 2013

DOI: 10.1002/anie.201306093