α- and β-Lipomycin: total syntheses by sequential stille couplings and assignment of the absolute configuration of all stereogenic centers.

40 years ago spectroscopy, derivatization, and degradation revealed the structures of α-lipomycin and its aglycon β-lipomycin except for the configurations of their side-chain stereocenters. We synthesized all relevant β-lipomycin candidates: the (12R,13S) isomer has the same specific rotational value as the natural product. By the same criterion the (12R,13S)-configured D-digitoxide is identical to α-lipomycin. We double-checked our assignments by degrading α- and β-lipomycin to the diesters 33 and 34 and proving their 3D structures synthetically. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Citation

Max L Hofferberth, Reinhard Brückner. α- and β-Lipomycin: total syntheses by sequential stille couplings and assignment of the absolute configuration of all stereogenic centers. Angewandte Chemie (International ed. in English). 2014 Jul 7;53(28):7328-34

PMID: 24895187

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