Kinetically controlled E-selective catalytic olefin metathesis
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Author(s)
Nguyen, Thach T.
Koh, Ming Joo
Shen, Xiao
Romiti, Filippo
Hoveyda, Amir H.
Schrock, Richard Royce
Date Issued
April 2016
Journal
Science
Publisher
American Association for the Advancement of Science (AAAS)
Citation
Nguyen, Thach T., Ming Joo Koh, Xiao Shen, Filippo Romiti, Richard R. Schrock, and Amir H. Hoveyda. “Kinetically controlledE-Selective Catalytic Olefin Metathesis.” Science 352, no. 6285 (April 28, 2016): 569–575.
Version
Author's final manuscript
Abstract
A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity. With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1126/SCIENCE.AAF4622
