η3-Pyranyl and η3-Pyridinyl Molybdenum π-Complexes as Chiral Scaffolds for the Enantioselective Construction of Substituted Oxa- and Aza[3.3.1]bicyclics: First Enantio- and Regiocontrolled [5+3] Cycloaddition Reactions

作者: Ramón Gómez Arrayás , Lanny S. Liebeskind

DOI: 10.1021/JA035424I

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摘要: The first Mo-mediated [5+3] cycloadditions are reported. 3-Substituted pyranyl and pyridinyl molybdenum π-complexes participate in enantiocontrolled provide a new efficient synthetic approach to oxa- aza[3.3.1]bicyclics of high enantiomeric purity. reaction proceeds good excellent yields with complete regio- endo-selectivities; it diverts [2+3] cycloaddition pathway when 2-substituted heterocycle used. This methodology, coupled variety general demetalation protocols, holds much promise applications.

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