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
- 1 July 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (30) , 9026-9027
- https://doi.org/10.1021/ja035424i
Abstract
The first Mo-mediated [5+3] cycloadditions are reported. 3-Substituted pyranyl and pyridinyl molybdenum pi-complexes participate in enantiocontrolled [5+3] cycloadditions and provide a new and efficient synthetic approach to oxa- and aza[3.3.1]bicyclics of high enantiomeric purity. The reaction proceeds in good to excellent yields and with complete regio- and endo-selectivities; it diverts to a [2+3] cycloaddition pathway when 2-substituted heterocycle pi-complexes are used. This methodology, coupled with a variety of general demetalation protocols, holds much promise in synthetic applications.Keywords
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