Two Syntheses of dl-Aplysistatin

Thomas R Hoye, Andrew J. Caruso, Joseph F. Dellaria, Mark J. Kurth

Research output: Contribution to journalArticlepeer-review

39 Scopus citations

Abstract

dl-Aplysistatin (1) was synthesized by two independent routes. The first (Scheme II) proceeded in seven steps and 4% yield from homogeraniol, utilized the mercuric ion mediated brominative cyclization of diene 2 as the key transformation, but lacked stereocontrol over the relationship between C12 and the A-ring stereocenters. The second synthesis (Scheme III) was achieved in eight steps and 31% yield from lactone 10, involved the aldol reaction of tert-butyl crotonate enolate anion with a single face of the aldehyde derived from hemiacetal 11, and allowed high 1,3-diastereoselectivity in the Hg(II)-induced cyclization of alcohols 20. Difference NOE spectroscopy played an important role in the deduction of stereochemistry in lactones 24.

Original languageEnglish (US)
Pages (from-to)6704-6709
Number of pages6
JournalJournal of the American Chemical Society
Volume104
Issue number24
DOIs
StatePublished - Jan 1 1982

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