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Enantiodivergent Synthesis of Allenes by Point-to-Axial Chirality Transfer.

ABSTRACT: An enantiodivergent method for the synthesis of multiply substituted allenes is described. Highly enantioenriched, point-chiral boronic esters were synthesized by homologation of ?-seleno alkenyl boronic esters with lithiated carbamates and eliminated to form axially chiral allene products. By employing either oxidative or alkylative conditions, both syn and anti elimination could be achieved with complete stereospecificity. The process enables the synthesis of either M or P?allenes from a single isomer of a point-chiral precursor and can be employed for the enantioselective assembly of di-, tri-, and tetrasubstituted allenes.

SUBMITTER: Armstrong RJ

PROVIDER: S-EPMC6033179 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Enantiodivergent Synthesis of Allenes by Point-to-Axial Chirality Transfer.

Armstrong Roly J RJ Nandakumar Meganathan M Dias Rafael M P RMP Noble Adam A Myers Eddie L EL Aggarwal Varinder K VK

Angewandte Chemie (International ed. in English) 20180530 27

An enantiodivergent method for the synthesis of multiply substituted allenes is described. Highly enantioenriched, point-chiral boronic esters were synthesized by homologation of α-seleno alkenyl boronic esters with lithiated carbamates and eliminated to form axially chiral allene products. By employing either oxidative or alkylative conditions, both syn and anti elimination could be achieved with complete stereospecificity. The process enables the synthesis of either M or P allenes from a singl ...[more]

PMID: 29719111

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