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Stereoselective synthesis of the C14-C23 fragment of biselyngbyolide A and B enabled by transition metal catalysis.

ABSTRACT: Transition met al catalysis has enabled the highly stereoselective and protecting group-free synthesis of the C14-C23 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 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.

SUBMITTER: Thorat RG

PROVIDER: S-EPMC6327972 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Stereoselective synthesis of the C14-C23 fragment of biselyngbyolide A and B enabled by transition metal catalysis.

Thorat Rakesh G RG Brooks Bailey A BA Nichols Brandon B Harned Andrew M AM

Tetrahedron 20181102 51

Transition met al catalysis has enabled the highly stereoselective and protecting group-free synthesis of the C14-C23 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 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-cata ...[more]

PMID: 30636818

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