Iodine Activation of Alcohols: A Computational Study
Document Type
Article
Publication Date
6-1-2018
Abstract
Abstract: A DFT study aimed at unravelling the origin of catalytic activity of iodine in reaction with alcohols is presented. Computed free energies for generation of the O–I complexes from the separated reactants are around 3 kcal/mol and solvation increases endoergicity by ca. 1 kcal/mol. Calculations suggest that halogen bond formation between I2 and alcohols does not lead to strong activation of the hydroxyl as a leaving group, although solvent has a notable effect in lowering endoergicity for carbocation formation. Model tertiary alcohols exhibited β-proton abstraction following breaking of the C–O bond, while model secondary and primary alcohols experienced an earlier β-proton abstraction, synchronic with the C–O bond cleavage. Consistent with computed natural bond orbital charges, benzylic and propargylic alcohols underwent iodide anion quenching at the para position of phenyl and C-3, respectively. Graphical Abstract: [Figure not available: see fulltext.].
Publication Title
Topics in Catalysis
Volume
61
Issue
7-8
First Page
636
Last Page
642
Digital Object Identifier (DOI)
10.1007/s11244-018-0918-1
ISSN
10225528
Citation Information
Borosky, Stavber, S., & Laali, K. K. (2018). Iodine Activation of Alcohols: A Computational Study. Topics in Catalysis, 61(7-8), 636–642. https://doi.org/10.1007/s11244-018-0918-1