Crossmetathesis of vinyl halides: Scope and limitation of ruthenium-based catalysts.

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The phosphine-free “second-generation” Blechert/Hoveyda−Grubbs catalyst Ru(═C(H)C6H4-o-O-i-Pr)(H2IMes)Cl2 (H2IMes = 4,5-dihydro-1,3-dimesitylimidazol-2-ylidene) and Piers catalyst [Ru(═CHPCy3)(H2IMes)Cl2]BF4 (Cy = cyclo-C6H11) for olefin metathesis effected cross-metathesis (CM) of vinyl chloride and 1,2-dichloroethene with several unhindered terminal and internal alkenes in up to 95% yield (5 mol % catalyst). In most cases, 1,2-dichloroethene was more successful than vinyl chloride. Ring-opening CM of cyclooctene provided greater yields than CM: with vinyl chloride, 93% yield; with 1,2-dichloroethene, >95%. Other common Ru-based catalysts failed to effect CM under similar conditions, but instead underwent rapid decomposition. The dimeric ruthenium-monochloromethylidene complex [Ru(═CHCl)(H2IMes)Cl(μ-Cl)]2 was isolated as a thermally unstable intermediate. CM reactions with 1,2-dibromoethene afforded 22% CM product in the best case; halide exchange with the catalyst was significant. CM reactions involving vinyl fluoride typically led to <3 >turnovers, but the dimeric intermediate [Ru(═CHF)(H2IMes)Cl(μ-Cl)]2 was sufficiently long-lived to be characterized by single-crystal X-ray diffraction. Ring-opening CM of cyclooctene with vinyl fluoride (55% yield) was more favorable than CM.




Macnaughtan, M. L.; Gary, J . B.; Gerlach, D. L.; Johnson, M. J. A.; Kampf, J. W. "Crossmetathesis of vinyl halides: Scope and limitation of ruthenium-based catalysts." Organometallics. 2009, 28, 2880-2887.



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