Facile solvolysis of a surprisingly twisted tertiary amide. (12th January 2016)

• Record Type: Journal Article
• Authors: Bloomfield, Aaron J.; Chaudhuri, Subhajyoti; Mercado, Brandon Q.; Batista, Victor S.; Crabtree, Robert H.
• Is Part Of: New journal of chemistry. Volume 40:Number 3(2016:Mar.)
• Page Start: 1974
• Page End: 1981
• Publication Date: 2016-01-12
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c5nj02449h
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : A twisted 3° amide is cleaved at the same rate as a methyl ester under alkaline conditions at 22 °C. Abstract : A bicyclo[2.2.2]octane derivative containing both a tertiary amide and a methyl ester (1 ) was shown crystallographically to adopt a conformation in which the amide is in the cis configuration, which is sterically disfavored, but electronically favored. The steric strain induces a significant torsion (15.9°) of the amide, thereby greatly increasing the solvolytic lability of the amide to the extent that we see competitive amide solvolysis in the presence of the normally more labile methyl ester also present in the molecule.