Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis
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Nguyen et al. Text TSCM FINAL.pdf
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Author(s)
Nguyen, Thach T.
Koh, Ming Joo
Mann, Tyler J.
Hoveyda, Amir H.
Schrock, Richard Royce
Date Issued
December 2017
Journal
Nature
Publisher
Nature Publishing Group
Citation
Nguyen, Thach T. et al. “Synthesis of E- and Z-Trisubstituted Alkenes by Catalytic Cross-Metathesis.” Nature 552, 7685 (December 2017): 347–354
Version
Author's final manuscript
Abstract
Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity—namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products—and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1038/nature25002
