Generation and trapping of cyclopentenylidene gold species: four pathways to polycyclic compounds.
Cyclopentenylidene gold complexes can easily be formed from vinyl allenes through a Nazarov-like mechanism. Such carbenes may transform in four different ways into polycyclic frameworks: electrophilic cyclopropanation, C-H insertion, C-C migration, or proton shift. We have studied the selectivity of these different pathways and used our findings for the expedient preparation of valuable complex molecules. An application to the total synthesis of a natural product, Delta(9(12))-capnellene, is presented. DFT computations were carried out to shed light on the mechanisms.
Lemière
Gilles
G
UPMC Paris 06, Laboratoire de Chimie Organique (UMR CNRS 7611), Institut de Chimie Moléculaire (FR 2769), case 229, 4 place Jussieu, F-75252 Paris cedex 05, France.
Gandon
Vincent
V
Cariou
Kevin
K
Hours
Alexandra
A
Fukuyama
Takahide
T
Dhimane
Anne-Lise
AL
Fensterbank
Louis
L
Malacria
Max
M