title: Generation and trapping of cyclopentenylidene gold species: four pathways to polycyclic compounds.
abstract: 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.
authors.affiliation: 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.
authors.forename: Gilles
authors.initials: G
authors.lastname: Lemière
authors.forename: Vincent
authors.initials: V
authors.lastname: Gandon
authors.forename: Kevin
authors.initials: K
authors.lastname: Cariou
authors.forename: Alexandra
authors.initials: A
authors.lastname: Hours
authors.forename: Takahide
authors.initials: T
authors.lastname: Fukuyama
authors.forename: Anne-Lise
authors.initials: AL
authors.lastname: Dhimane
authors.forename: Louis
authors.initials: L
authors.lastname: Fensterbank
authors.forename: Max
authors.initials: M
authors.lastname: Malacria