| Abstract
| - First, an efficient method for the synthesis of optically enriched N-fused bicyclic structures isreported. Through Mo-catalyzed desymmetrization of readily available achiral polyene substrates, 5,6-,5,7-, and 5,8-bicyclic amides can be synthesized in up to >98% ee. The effects of catalyst structure, olefinsubstitution, positioning of Lewis basic functional groups and ring size are examined and discussed indetail. In the second phase of investigations, a catalytic asymmetric method for highly enantioselective (upto 97% ee) synthesis of small- and medium-ring unsaturated cyclic amines is reported; optically enrichedproducts bear a secondary amine or a readily removable Cbz or acetamide unit. Regio- and diastereoselective functionalizations of olefins within the optically enriched amine products have been carried out.Both catalytic asymmetric methods include transformations that lead to the formation of trisubstituted aswell as disubstituted cyclic alkenes. The protocols outlined herein afford various cyclic amines of highoptical purity; such products are not easily accessed by alternative protocols and can be used inenantioselective total syntheses of biologically active molecules.
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