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

TETRAHEDRON

卷:74

Article

Thorat, Rakesh G.¹  Brooks, Bailey A.¹  Nichols, Brandon¹  Harned, Andrew M.¹ 

[1] Texas Tech Univ, Dept Chem & Biochem, 1204 Boston Ave, Lubbock, TX 79409 USA

关键词: Stille reaction.;    Oxidation;    Allylation;    Stereoselectivity;    Catalysis;   

DOI  :  10.1016/j.tet.2018.10.066

来源: Elsevier

【 摘 要 】

Transition metal 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 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. (C) 2018 Elsevier Ltd. All rights reserved.

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