| Abstract
| - An atom economic, selective, and highly practical two-metal one-pot synthesis of heterocycleshas been developed that efficiently affords enantio- and diastereopure N- and O-heterocyclic products.Furthermore, use of a chiral catalyst in the two-metal procedure allows formation of all possiblediastereomers, even those that are traditionally difficult to access via cyclization routes due to thermodynamics. Interestingly, the nature of the enantiodiscriminating event differs between the use of amine versusalcohol nucleophiles. The method also affords heterocyclic products that are synthetically usefulintermediates. Through the Z-vinylsilane a variety of stereodefined trisubstituted olefin products can beaccessed including several all-carbon motifs. Finally, the utility of these heterocyclic products in totalsynthesis is demonstrated through concise syntheses of a kainoid intermediate, a constituent of oil of rose,and the ring B portion of bryostatin, a potent chemotherapeutic.
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