One-pot methylenation-Heck coupling reactions

ORGN 136

Lise Brethous, lisebrethous@hotmail.com and Hélène Lebel, lebelhe@chimie.umontreal.ca. Département de Chimie, Université de Montréal, PO Box 6128, Station Downtown, Montréal, QC H3T1J4, Canada

Our research group has recently reported a new efficient copper and rhodium catalyzed methylenation of carbonyl derivatives using TMSCHN2, i-PrOH, Ph3P. We have also devised multicatalytic strategies to in-situ derivatized the terminal alkenes.  Along these lines, this paper will feature a new methylenation-Heck coupling multicatalytic tandem reactions which lead to the formation of substituted alkenes directly from carbonyl compounds. Copper catalyzed-methylenation reaction with benzaldehyde derivatives led to the formation of the corresponding styrenes, which are then in-situ submitted to the palladium-catalyzed Heck coupling reaction. This one-pot sequence avoided the isolation of volatile styrene intermediates, and decreased also the amount of by-products. We have used this one-pot process to synthesize biologicaly active stilbene derivatives such as the resveratrol analogues.  Furthermore, the extension of this method to an intramolecular process will be also presented.