Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis
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Direct synthesis.pdf
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Author(s)
Koh, Ming Joo
Nguyen, Thach T.
Zhang, Hanmo
Hoveyda, Amir H.
Schrock, Richard Royce
Date Issued
March 2016
Journal
Nature
Publisher
Nature Publishing Group
Citation
Koh, Ming Joo et al. “Direct Synthesis of Z-Alkenyl Halides through Catalytic Cross-Metathesis.” Nature 531.7595 (2016): 459–465.
Version
Author's final manuscript
Abstract
Olefin metathesis has had a large impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is limited. Here we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high conversion at ambient temperature within four hours. We obtain many alkenyl chlorides, bromides and fluorides in up to 91 per cent yield and complete Z selectivity. This method can be used to synthesize biologically active compounds readily and to perform site- and stereoselective fluorination of complex organic molecules.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1038/nature17396
