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.
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January 2018
A rapid synthesis of the C1-C13 fragment of biselynbyolide A and B is reported. The judicious use of catalytic transformations for C-C bond formation and stereocenter generation greatly minimizes the use of protecting groups and oxidation state changes, as compared to previously reported routes to similar fragments.
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