期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 12, 期 23, 页码 5916-5923出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200600174
关键词
alkynes; cyclization; density functional calculations; gold; rearrangement
Three pathways actually compete in metal-catalyzed cyclizations of enynes in which the metal selectively activates the alkyne: an endocyclic process and two exo-cyclizations, one proceeding by anti attack of the alkene and a second one resulting in a syn addition. Although cyclobutenes may be formed in transition-metal-catalyzed cyclization of some enynes, particularly, 1,7-enynes. these compounds are not necessarily the intermediates in the skeletal rearrangement. Cyclobutenes are formed by ring expansion of syn-cyclopropyl metal-carbenes formed in the syn pathway.
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