Chagosensine: A Riddle Wrapped in a Mystery Inside an Enigma.

Journal of the American Chemical Society
Marc HeinrichAlois Fürstner

Abstract

The marine macrolide chagosensine is supposedly distinguished by a (Z,Z)-configured 1,3-chlorodiene contained within a highly strained 16-membered lactone ring, which also incorporates two trans-2,5-disubstituted tetrahydrofuran (THF) rings; this array is unique. After our initial synthesis campaign had shown that the originally proposed structure is incorrect, the published data set was critically revisited to identify potential mis-assignments. The "northern" THF ring and the anti-configured diol in the "southern" sector both seemed to be sites of concern, thus making it plausible that a panel of eight diastereomeric chagosensine-like compounds would allow the puzzle to be solved. To meet the challenge, the preparation of the required building blocks was optimized, and a convergent strategy for their assembly was developed. A key role was played by the cobalt-catalyzed oxidative cyclization of alken-5-ol derivatives ("Mukaiyama cyclization"), which is shown to be exquisitely chemoselective for terminal alkenes, leaving even terminal alkynes (and other sites of unsaturation) untouched. Likewise, a palladium-catalyzed alkyne alkoxycarbonylation reaction with formation of an α-methylene-γ-lactone proved instrumental, which had n...Continue Reading

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Citations

Sep 19, 2020·Angewandte Chemie·Saskia SchulthoffAlois Fürstner
Dec 9, 2020·Angewandte Chemie·Lorenz E LöfflerAlois Fürstner
Jan 16, 2021·Angewandte Chemie·Bart HerléAlois Fürstner
Jan 16, 2021·Angewandte Chemie·Georg Späth, Alois Fürstner
Jun 25, 2021·Chemical Science·Shota KatoHaruhiko Fuwa
Jul 10, 2021·Chemistry : a European Journal·Romain MelotAlois Fürstner
Nov 5, 2020·Journal of the American Chemical Society·Franck Le VaillantJosep Cornella

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

chagosensine

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