title: Intramolecular Pd(0)-catalyzed reactions of (2-iodoanilino)-aldehydes: a joint experimental-computational study.
abstract: An extensive joint experimental-computational density functional theory (DFT) study has been carried out to gain insight into the factors that control the chemoselectivity (i.e., acylation vs α-arylation reaction) of palladium-catalyzed cyclizations of (2-iodoanilino)-aldehydes. To this end, the nature of the tethers joining the aniline nitrogen and the aldehyde moiety, different palladium precatalysts and reaction conditions (base and temperature), as well as different additives (mono- and bidendate ligands) has been explored. The adequate selection of these variables allows for the control of the selectivity of the process. Thus, (2-iodoanilino)-aldehydes generally lead to the formation of nucleophilic addition derived products when Cs(2)CO(3)/Et(3)N is used as base. In contrast, the use of stronger bases like K(t)OBu (in the presence of PhOH) mainly forms α-arylation reaction products. The different reaction pathways leading to the experimentally observed reaction products have been studied by means of computational tools.
authors.affiliation: Laboratori de Química Orgànica, Facultat de Farmàcia, and Institut de Biomedicina, Universitat de Barcelona, 08028-Barcelona, Spain. dsole@ub.edu
authors.forename: Daniel
authors.initials: D
authors.lastname: Solé
authors.forename: Francesco
authors.initials: F
authors.lastname: Mariani
authors.forename: Israel
authors.initials: I
authors.lastname: Fernández
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Sierra
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000814:Aniline Compounds / Q000737:chemistry*; D002384:Catalysis; D003198:Computer Simulation; D008024:Ligands; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000814:Aniline Compounds; D008024:Ligands; D010165:Palladium