1,2-Redox Transpositions of Tertiary Amides

Abstract

Reactions capable of transposing the oxidation levels of adjacent carbon atoms in organic molecules enable rapid and fundamental alteration of a molecule’s reactivity. Herein, we report the 1,2-transposition of carbon atom oxidation level in cyclic and acyclic tertiary amides, resulting in the one-pot synthesis of 1,2- and 1,3-oxygenated tertiary amines. This oxidation level transfer was facilitated by the careful orchestration of an iridium-catalyzed reduction with the functionalization of transiently-formed enamine intermediates. Remarkably, a novel 1,2-carbonyl transposition was observed when the commercial oxidant mCPBA was selected as the coupling partner. The scope of this transformation and the breadth of this redox transposition strategy has been explored and the diverse β-functionalized amine products were shown to be multi-faceted and valuable synthetic intermediates, accessing challenging biologically-relevant motifs.

Late-Stage Molecular Editing Enabled by Ketone Chain-Walking Isomerization

“…This elegant process is kinetically controlled but is irreversible and limited to 1,2-transpositions. Thus, a reversible carbonyl chain-walking process akin to alkene chain-walking would open new synthetic opportunities …”

“…Thus, a reversible carbonyl chain-walking process akin to alkene chain-walking would open new synthetic opportunities. 11 …”