title: C2-Alkylation and Alkenylation of Indoles Catalyzed by a Low-Valent Cobalt Complex in the Absence of Reductant.
abstract: Herein an extremely versatile, well-defined, low-valent cobalt catalyst [Co(PMe3)4] capable of intermolecular and intramolecular imine-directed C2-alkylation and alkenylation of indoles is reported. The reaction proceeds in the absence of reducing agents or additives, affording a range of substituted indoles and dihydropyrroloindoles in high yields and regioselectivities. With the aid of deuterium labeling studies and DFT (Density Functional Theory) calculations, a mechanism is proposed that is based on a Ligand-to-Ligand Hydrogen Transfer pathway.
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Brendan J
authors.initials: BJ
authors.lastname: Fallon
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Etienne
authors.initials: E
authors.lastname: Derat
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Muriel
authors.initials: M
authors.lastname: Amatore
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Corinne
authors.initials: C
authors.lastname: Aubert
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Fabrice
authors.initials: F
authors.lastname: Chemla
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Franck
authors.initials: F
authors.lastname: Ferreira
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Alejandro
authors.initials: A
authors.lastname: Perez-Luna
authors.affiliation: UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Marc
authors.initials: M
authors.lastname: Petit