Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis
Author(s)Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Hoveyda, Amir H.; Schrock, Richard Royce
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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.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Nature Publishing Group
Koh, Ming Joo et al. “Direct Synthesis of Z-Alkenyl Halides through Catalytic Cross-Metathesis.” Nature 531.7595 (2016): 459–465.
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