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Stereoselective synthesis of the C14C23 fragment of biselyngbyolide A and B enabled by transition metal catalysis

Author:
Thorat, Rakesh G., Brooks, Bailey A., Nichols, Brandon, Harned, Andrew M.
Source:
Tetrahedron 2018 v.74 no.51 pp. 7277-7281
ISSN:
0040-4020
Subject:
Stille reaction, aldehydes, allylation, carbonates, catalytic activity, chemical structure, oxidation, palladium, stereochemistry, stereoselective synthesis, stereoselectivity
Abstract:
Transition metal catalysis has enabled the highly stereoselective and protecting group-free synthesis of the C14C23 fragment of the apoptosis-inducing natural products biselyngbyolide A and B. A Pd-catalyzed Stille reaction between a vinyl stannane and a crotyl carbonate formed the skipped diene with complete control of the trisubstituted bond and excellent control over the branched/linear products. A Cu-catalyzed Stahl oxidation was used to form the requisite aldehyde needed for a Ag-catalyzed asymmetric allylation. The latter provided the final fragment with excellent stereochemical control.
Agid:
6232083