Structure elucidation and progress toward the total synthesis of (+)-trienomycin A

Chapter one of this dissertation describes the structure elucidation of (+)- trienomycin A (1). The relative and absolute stereochemistry of (+)-trienomycin A was established by degradative and synthetic study and were assigned as 3R, 11S, 12R, and 13R. Chapter two describes the progress towards the total synthesis of (+)-trienomycin A. The central features of the synthesis involve: (1) Development of an efficient route for the asymmetric synthesis of keto-aldehyde (+)-33. (2) Construction the trisubstituted cis C(14)-C(15) double bond by conjugate addition of methyl cuprate to acetylenic ester 81 and furnishing the synthesis of allyl chloride 85. (3) Synthesis of northeastern subunit-sulfone aminal 51, with the correct C(3)-R configuration. (4) Union of sulfone aminal 51 and allyl iodide 86 to afford advanced intermediate 49. (Abstract shortened by UMI.