Intramolecular hydride transfer onto arynes: redox-neutral and transition metal-free C(sp3)–H functionalization of amines. Issue 11 (20th February 2018)

• Record Type: Journal Article
• Authors: Idiris, Fahima I. M.; Majesté, Cécile E.; Craven, Gregory B.; Jones, Christopher R.
• Is Part Of: Chemical science. Volume 9:Issue 11(2018)
• Page Start: 2873
• Page End: 2878
• Publication Date: 2018-02-20
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c8sc00181b
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Novel intramolecular hydride transfer onto arynes is exploited in a redox-neutral intermolecular α-functionalization of amines with diverse pronucleophiles. Abstract : Transition metal-free intramolecular hydride transfer onto arynes is reported for the first time. This unique transformation is utilized in redox-neutral intermolecular α-functionalization reactions of different tertiary amines, generating C(sp 3 )–C(sp 3 /sp 2 /sp) bonds in a single synthetic operation. Deuterium labeling studies support initial cleavage of the α-C–H bond via intramolecular 1, 5-hydride transfer onto the aryne, which leads to activation of a range of integrated pronucleophiles and ultimately affords a new approach to cross-dehydrogenative coupling reactions which utilize aryne intermediates.