A Convergent Synthetic Route to the Tunicamycin Antiobiotics. Synthesis of (+)-Tunicamycin V

Citation

Gin, David Y. (1994) A Convergent Synthetic Route to the Tunicamycin Antiobiotics. Synthesis of (+)-Tunicamycin V. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/p6qx-ng34. https://resolver.caltech.edu/CaltechTHESIS:05072013-095813413

Abstract

A concise synthetic route to the tunicamycin antibiotics is described, illustrated by the preparation of (+)-tunicamycin-V (1-V). Key features of the synthesis include: (1) the development and application of a silicon-mediated reductive coupling of aldehydes and allylic alcohols to construct the undecose core of the natural product; and (2) the development of an efficient procedure for the synthesis of the trehalose glycosidic bond within the antibiotic. These innovations allow for the coupling of a uridine-derived aldehyde fragment with a preformed trehalose-linked disaccharide allylic alcohol to form the carbohydrate core (1) of the natural product in a highly convergent manner. The resultant amino polyol is a versatile intermediate for the synthesis of any of the homologous tunicamycin antibiotics.

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