Ruthenium catalyzed enyne cycloisomerizations and hydroxycyclizations with skeletal rearrangement

A neutral arene-tethered ruthenium complex was found to be a catalyst precursor for enyne cycloisomerizations and hydroxycyclizations. The observed products were the result of a skeletal rearrangement process, and include an unusual cyclization to form a six-membered ring. Labeling studies on the six-membered ring product are in accord with an electrophilic activation mechanism that proceeds via cationic cyclopropyl carbene intermediates. (c) 2006 Elsevier B.V. All rights reserved.