Hydrocarbation of CC Bonds: Quantification of the Nucleophilic Reactivity of Ynamides1. Issue 19 (8th April 2014)

• Record Type: Journal Article
• Authors: Laub, Hans A.; Evano, Gwilherm; Mayr, Herbert
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 19(2014)
• Page Start: 4968
• Page End: 4971
• Publication Date: 2014-04-08
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201402055
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Donor‐substituted diarylcarbenium ions Ar₂CH⁺ 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 CH bond across the CC 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 <italic>k</italic>₂, 20 °C) with the electrophilicity parameters <italic>E</italic> of the diarylcarbenium ions allow us to include ynamides in our comprehensive nucleophilicity scale and thus predict potential electrophilic reaction partners.</p> </abstract>