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Total Synthesis and Structural Revision of (+)‐Uprolide G Acetate
Author(s) -
Zhu Liangyu,
Liu Yuan,
Ma Renze,
Tong Rongbiao
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201409618
Subject(s) - metathesis , total synthesis , chemistry , salt metathesis reaction , stereochemistry , dihydroxylation , ring closing metathesis , combinatorial chemistry , enantioselective synthesis , organic chemistry , catalysis , polymerization , polymer
The first, asymmetric total synthesis of the proposed structure of (+)‐uprolide G acetate (UGA) is reported, and the spectral properties of the synthetic compound clearly differed from those reported for natural UGA. On the basis of comprehensive analysis of the NMR data, two possible structures for the natural UGA were proposed and their total synthesis achieved, thus leading to the identification and confirmation of the correct structure and absolute configuration of the natural UGA. This synthesis was enabled by development of a novel synthetic strategy, which revolved around three key cyclization reactions: an Achmatowicz rearrangement, Sharpless asymmetric dihydroxylation/lactonization, and ring‐closing metathesis. These synthetic studies pave the way for further studies on this class of structurally unusual cytotoxic cembranolides.