1,2-Redox Transpositions of Tertiary Amides

• Published in: Journal of the American Chemical Society Vol. 145; no. 40; pp. 21745 - 21751
• Main Authors: Shennan, Benjamin D. A., Sánchez-Alonso, Sergio, Rossini, Gabriele, Dixon, Darren J.
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 11.10.2023; Amer Chemical Soc
• Subjects: amides; amino alcohols; carbon; Chemistry; Chemistry, Multidisciplinary; Communication; enamines; oxidation; Physical Sciences; Science & Technology; synthesis; OXIDATION; REARRANGEMENT; REDUCTIVE FUNCTIONALIZATION; SUBSTITUTION; ALPHA-HYDROXY KETONES; HYDROBORATION; HETEROCYCLES; AMINES; ENAMINES; BETA-POSITION
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.3c08466

Reactions capable of transposing the oxidation levels of adjacent carbon atoms enable rapid and fundamental alteration of a molecule’s reactivity. Herein, we report the 1,2-transposition of the 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. A novel 1,2-carbonyl transposition is described, and the breadth of this redox transposition strategy has been further explored by the development of aminoalcohol and enaminone syntheses. The diverse β-functionalized amine products were shown to be multifaceted and valuable synthetic intermediates, accessing challenging biologically relevant motifs.