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Preparation of anti-vicinal amino alcohols: asymmetric synthesis of D-erythro-sphinganine, (+)-spisulosine, and D-ribo-phytosphingosine.

ABSTRACT: Two variations of the Overman rearrangement have been developed for the highly selective synthesis of anti-vicinal amino alcohol natural products. A MOM ether-directed palladium(II)-catalyzed rearrangement of an allylic trichloroacetimidate was used as the key step for the preparation of the protein kinase C inhibitor D-erythro-sphinganine and the antitumor agent (+)-spisulosine, whereas the Overman rearrangement of chiral allylic trichloroacetimidates generated by the asymmetric reduction of an ?,?-unsaturated methyl ketone allowed rapid access both to D-ribo-phytosphingosine and L-arabino-phytosphingosine.

SUBMITTER: Calder ED

PROVIDER: S-EPMC3719175 | biostudies-literature | 2013 Jul

REPOSITORIES: biostudies-literature

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Preparation of anti-vicinal amino alcohols: asymmetric synthesis of D-erythro-sphinganine, (+)-spisulosine, and D-ribo-phytosphingosine.

Calder Ewen D D ED Zaed Ahmed M AM Sutherland Andrew A

The Journal of organic chemistry 20130703 14

Two variations of the Overman rearrangement have been developed for the highly selective synthesis of anti-vicinal amino alcohol natural products. A MOM ether-directed palladium(II)-catalyzed rearrangement of an allylic trichloroacetimidate was used as the key step for the preparation of the protein kinase C inhibitor D-erythro-sphinganine and the antitumor agent (+)-spisulosine, whereas the Overman rearrangement of chiral allylic trichloroacetimidates generated by the asymmetric reduction of an ...[more]

PMID: 23795558

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