Shennan Benjamin D A, Sánchez-Alonso Sergio, Rossini Gabriele, Dixon Darren J
Department of Chemistry, University of Oxford, Chemical Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, U.K.
J Am Chem Soc. 2023 Oct 11;145(40):21745-21751. doi: 10.1021/jacs.3c08466. Epub 2023 Sep 27.
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.
能够改变相邻碳原子氧化态的反应能够快速且根本性地改变分子的反应活性。在此，我们报道了环状和非环状叔酰胺中碳原子氧化态的1,2-迁移，从而实现了1,2-和1,3-氧化叔胺的一锅法合成。通过精心设计铱催化的还原反应与瞬态形成的烯胺中间体的官能化反应，促进了这种氧化态转移。本文描述了一种新型的1,2-羰基迁移，并通过氨基醇和烯胺酮合成的发展进一步探索了这种氧化还原迁移策略的广度。结果表明，多种β-官能化胺产物是多面且有价值的合成中间体，可用于构建具有挑战性的生物相关基序。
