Premium
Enantioselective Total Synthesis of (+)‐Steenkrotin A and Determination of Its Absolute Configuration
Author(s) -
Pan Saiyong,
Gao Beiling,
Hu Jialei,
Xuan Jun,
Xie Hujun,
Ding Hanfeng
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503831
Subject(s) - total synthesis , enantioselective synthesis , aldol reaction , absolute configuration , intramolecular force , stereocenter , chemistry , stereochemistry , yield (engineering) , aldol condensation , organic chemistry , catalysis , materials science , metallurgy
Abstract The first enantioselective total synthesis of (+)‐steenkrotin A has been achieved in 18 steps and 4.2 % overall yield. The key features of the strategy entail a Rh‐catalyzed O−H bond insertion followed by an intramolecular carbonyl‐ene reaction, two sequential SmI 2 ‐mediated Ueno–Stork and ketyl–olefin cyclizations, and a cascade intramolecular aldol condensation/vinylogous retro‐aldol/aldol process with inversion of the relative configuration at the C7 position. The absolute configuration of (+)‐steenkrotin A was determined based on the stepwise construction of the stereocenters during the total synthesis.