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Journal of the American Chemical Society

The design and mechanism of palladium catalysts for synthesis of methylene lactones by cyclocarbonylation of acetylenic alcohols

TF Murray, JR Norton

文献索引:Murray,T.F.; Norton,J.R. Journal of the American Chemical Society, 1979 , vol. 101, p. 4107 - 4119

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被引用次数: 85

摘要

Abstract: The Pd (I1)-catalyzed cyclocarbonylation of acetylenic alcohols to methylene lactones proceeds through carboalkoxypalladium intermediates, followed by intramolecular cis addition to the triple bond. Such intermediates have been independently synthesized, isolated, and found to undergo appropriate interconversions. AP~ I~/Bu~ P/CH~ CN catalyst system gives rates first order in CO pressure, with the rate-determining step evidently ...