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α‐ and β‐Lipomycin: Total Syntheses by Sequential Stille Couplings and Assignment of the Absolute Configuration of All Stereogenic Centers
Author(s) -
Hofferberth Max L.,
Brückner Reinhard
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201402255
Subject(s) - stereocenter , absolute configuration , derivatization , stille reaction , stereochemistry , chemistry , natural product , combinatorial chemistry , enantioselective synthesis , organic chemistry , high performance liquid chromatography , polymer , catalysis
Abstract 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 (12 R ,13 S ) isomer has the same specific rotational value as the natural product. By the same criterion the (12 R ,13 S )‐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.