Premium
Synthesis of Unsaturated Nine‐Membered Ring Ethers (Δ 3 ‐Oxonenes) Containing a Z ‐ or E ‐Configurated Double Bond: Thermodynamic versus Kinetic Control in Palladium‐Catalyzed Allylic Cyclizations
Author(s) -
Pohlmann Jens,
Sabater Christopher,
Hoffmann H. M. R.
Publication year - 1998
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/(sici)1521-3773(19980316)37:5<633::aid-anie633>3.0.co;2-8
Subject(s) - allylic rearrangement , double bond , catalysis , chemistry , palladium , ring (chemistry) , ligand (biochemistry) , ether , kinetic energy , medicinal chemistry , stereochemistry , polymer chemistry , organic chemistry , physics , biochemistry , receptor , quantum mechanics
Double stereocontrol is achieved in the Pd‐catalyzed cyclization of Δ 3 ‐oxonene precursors (see reactions outlined below). The configuration of the olefinic double bond and of the allylic carbon center α to the ether oxygen atom is dictated by the configuration of the double bond in the starting compound ( E/Z ), the Pd ligand (dppe = Ph 2 PCH 2 CH 2 PPh 2 ), and the reaction time.