Molybdenum chloride catalysts for Z-selective olefin metathesis reactions
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Author(s)
Koh, Ming Joo
Nguyen, Thach T.
Torker, Sebastian
Hoveyda, Amir H.
Lam, Jonathan K
Hyvl, Jakub
Schrock, Richard Royce
Date Issued
January 2017
Journal
Nature
Publisher
Nature Publishing Group
Citation
Koh, Ming Joo et al. “Molybdenum Chloride Catalysts for Z-Selective Olefin Metathesis Reactions.” Nature 542, 7639 (January 2017): 80–85 © 2017 Macmillan Publishers Limited, part of Springer Nature
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Author's final manuscript
Abstract
The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1038/NATURE21043
