The first total synthesis of (–)-lemonomycin and progress toward the total synthesis of (+)-cyanocycline A

Citation

Ashley, Eric Robert (2006) The first total synthesis of (–)-lemonomycin and progress toward the total synthesis of (+)-cyanocycline A. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-11152005-155011

Abstract

The first total synthesis of (–)-lemonomycin has been accomplished. The synthesis features a novel, auxiliary-controlled asymmetric dipolar cycloaddition, a highly convergent Suzuki coupling, a diastereoselective enamide hydrogenation to set the C(3) stereochemistry, and a convergent, efficient, and completely diastereoselective Pictet-Spengler cyclization with a glycosyloxy acetaldehyde. The total synthesis of (+)-cyanocycline A has been approached along two routes. Both routes feature dipolar cycloaddition reactions with alkyne-containing substrates and completely diastereoselective hydrogenations to set the C(4) stereochemistry. Proposals for the advancement of late-stage intermediates to the natural product are included.

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