Brønsted Base Prompted sp 3 C-H Latent Nucleophiles to Access α-Branched Amines Bearing β-Carbonyl by Cleaving Amide and Ester Bonds.

α-Branched amines are key motifs that exist in a plethora of natural products and pharmaceuticals. Herein we disclose the first convergent synthesis of α-branched amines bearing β-carbonyl in isoindolinones by employing unactivated tertiary amides and unactivated alkyl esters as benign electrophile sources. The reaction proceeds by the direct aroylation of a C( sp 3 )-H carbon adjacent to the nitrogen atom in core isoindolinones. Several amides and esters were screened to choose the potential acyl source for the substrate scope. The reaction is carried out with a repertoire of substrates under mild conditions and shows high functional group compatibility. Remarkably the reaction is amenable to organometallic ferrocenyl ester and indole methyl esters bearing an acidic NH moiety. Strikingly no trace of amidation product 8 is observed. In particular α-branched amines bearing β-carbonyl synthesized from indole methyl esters are considered important targets, as both motifs are prevalent in many drugs. This protocol is scalable, and products obtained from indole methyl esters show strong solid-state emission properties which are complementary with DFT calculations.