Catalytic Z-selective olefin cross-metathesis for natural product synthesis

Simon J. Meek, Robert V. O’Brien, Josep Llaveria, Richard R. Schrock and Amir H. Hoveyda ()
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Simon J. Meek: Merkert Chemistry Center, Boston College
Robert V. O’Brien: Merkert Chemistry Center, Boston College
Josep Llaveria: Merkert Chemistry Center, Boston College
Richard R. Schrock: Massachusetts Institute of Technology
Amir H. Hoveyda: Merkert Chemistry Center, Boston College

Nature, 2011, vol. 471, issue 7339, 461-466

Abstract: Abstract Alkenes are found in many biologically active molecules, and there are a large number of chemical transformations in which alkenes act as the reactants or products (or both) of the reaction. Many alkenes exist as either the E or the higher-energy Z stereoisomer. Catalytic procedures for the stereoselective formation of alkenes are valuable, yet methods enabling the synthesis of 1,2-disubstituted Z alkenes are scarce. Here we report catalytic Z-selective cross-metathesis reactions of terminal enol ethers, which have not been reported previously, and of allylic amides, used until now only in E-selective processes. The corresponding disubstituted alkenes are formed in up to >98% Z selectivity and 97% yield. These transformations, promoted by catalysts that contain the highly abundant and inexpensive metal molybdenum, are amenable to gram-scale operations. Use of reduced pressure is introduced as a simple and effective strategy for achieving high stereoselectivity. The utility of this method is demonstrated by its use in syntheses of an anti-oxidant plasmalogen phospholipid, found in electrically active tissues and implicated in Alzheimer’s disease, and the potent immunostimulant KRN7000.

Date: 2011
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DOI: 10.1038/nature09957

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