Premium
Hydrocarbation of CC Bonds: Quantification of the Nucleophilic Reactivity of Ynamides
Author(s) -
Laub Hans A.,
Evano Gwilherm,
Mayr Herbert
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201402055
Subject(s) - electrophile , iminium , nucleophile , chemistry , reactivity (psychology) , hydride , adduct , ion , medicinal chemistry , nucleophilic addition , computational chemistry , bond order , molecule , bond length , organic chemistry , metal , catalysis , medicine , alternative medicine , pathology
Donor‐substituted diarylcarbenium ions Ar 2 CH + react with ynamides to give 1‐amido‐substituted allyl cations (α,β‐unsaturated iminium ions). Kinetic studies show that these adducts, which correspond to the addition of a CH bond across the CC bond, are formed stepwise with initial formation of keteniminium ions and subsequent 1,3‐hydride shifts. The linear correlations between the second‐order rate constants (lg k 2 , 20 °C) with the electrophilicity parameters E of the diarylcarbenium ions allow us to include ynamides in our comprehensive nucleophilicity scale and thus predict potential electrophilic reaction partners.