Total Synthesis of the Antitumor Macrolides, (+)-Brefeldin A and 4‑Epi-Brefeldin A from D‑Glucose: Use of the Padwa Anionic Allenylsulfone [3+2]-Cycloadditive Elimination To Construct Trans-Configured Chiral Cyclopentane Systems

Ziyue Xiong, Karl J. Hale

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Abstract

A new synthesis of (+)-brefeldin A is reported via Padwa allenylsulfone [3+2]-cycloadditive elimination. Cycloadduct 13 was initially elaborated into iodide
27, which, following treatment with Zn, gave aldehyde 28 whose C(9) stereocenter was epimerized. Further elaboration into enoate 38 and Julia−Kocienski olefination with 5 subsequently afforded 39, which was deprotected at C(1) and O(15). Yamaguchi macrolactonization of the seco-acid thereafter afforded a macrocycle that underwent O-desilylation and inversion at C(4) to give (+)-brefeldin A following deprotection
Original languageEnglish
Pages (from-to)4254-4257
Number of pages4
JournalOrganic Letters
Volume18
Issue number17
Early online date19 Aug 2016
DOIs
Publication statusPublished - 2016

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Keywords

  • Brefeldin A, antitumour agent, [3+2]-cycloaddition, allenylsulfone, Mitsunobu inversion

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