Related Experiment Video
Updated: May 17, 2026

Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
Intramolecular Pd(0)-catalyzed reactions of (2-iodoanilino)-aldehydes: a joint experimental-computational study
Daniel Solé1, Francesco Mariani, Israel Fernández
1Laboratori de Química Orgànica, Facultat de Farmàcia, and Institut de Biomedicina, Universitat de Barcelona, 08028-Barcelona, Spain. dsole@ub.edu
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.
Related Concept Videos
Intramolecular Aldol Reaction
Radical Reactivity: Intramolecular vs Intermolecular
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
Aldehydes and Ketones with Amines: Imine Formation Mechanism
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism

