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Nickel-Catalyzed Regiodivergent Approach to Macrolide Motifs.

ABSTRACT: A strategy for regiochemical reversal of reductive macrocyclizations of aldehydes and terminal alkynes has been developed. Using an advanced synthetic intermediate directed towards the methymycin/neomethymycin class of macrolides, selective endocyclization provides the natural twelve-membered ring series, whereas ligand alteration enables selective exocyclization to provide access to the unnatural eleven-membered ring series. The twelve-membered ring adduct was converted to 10-deoxymethynolide, completing an efficient total synthesis of this natural product.

SUBMITTER: Shareef AR

PROVIDER: S-EPMC3377182 | biostudies-literature | 2012 Jan

REPOSITORIES: biostudies-literature

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Nickel-Catalyzed Regiodivergent Approach to Macrolide Motifs.

Shareef Abdur-Rafay AR Sherman David H DH Montgomery John J

Chemical science 20111206 3

A strategy for regiochemical reversal of reductive macrocyclizations of aldehydes and terminal alkynes has been developed. Using an advanced synthetic intermediate directed towards the methymycin/neomethymycin class of macrolides, selective endocyclization provides the natural twelve-membered ring series, whereas ligand alteration enables selective exocyclization to provide access to the unnatural eleven-membered ring series. The twelve-membered ring adduct was converted to 10-deoxymethynolide, ...[more]

PMID: 22737401

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