Premium
Synthesis of the Strychnos Alkaloid (−)‐Strychnopivotine and Confirmation of its Absolute Configuration
Author(s) -
Maertens Gaëtan,
Canesi Sylvain
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.201601319
Subject(s) - absolute configuration , desymmetrization , enantioselective synthesis , chemistry , circular dichroism , total synthesis , stereochemistry , heck reaction , stereoselectivity , combinatorial chemistry , organic chemistry , palladium , catalysis
The first enantioselective synthesis of (−)‐strychnopivotine from a known and inexpensive phenol has been achieved in 15 steps. The strategy is based on a new diastereoselective aza‐Michael‐enol‐ether cascade desymmetrization of a dienone, guided by a removable lactic acid‐derived chiral auxiliary. Synthesis involves a phenol dearomatization, a conjugated silicon addition, a stereoselective double reductive amination, and two Heck‐type carbopalladations as key steps. The absolute configuration of the natural compound, which, to date, has been uncertain, was confirmed by using circular dichroism (CD) spectroscopy and X‐ray analyses.