Department of Chemistry, Faculty of Sciences, Mersin University, 33343 Mersin, Turkey.
Process Research & Development, MRL, Merck & Co., Inc., 126 E Lincoln Avenue, Rahway, New Jersey 07065, United States.
J Org Chem. 2023 Jul 7;88(13):8874-8881. doi: 10.1021/acs.joc.3c00656. Epub 2023 Jun 9.
This article describes the development of a mild method for the -dealkylation of tertiary amines via photoredox catalysis and its application in late-stage functionalization. Using the developed method, more than 30 diverse aliphatic, aniline-type, and complex substrates are shown to undergo -dealkylation, providing a method with broader functional group tolerance compared to methods found in the literature. The scope also includes tertiary and secondary amine molecules with complex substructures and drug substrates. Interestingly, α-oxidation to imines was observed in several cyclic substructures instead of -dealkylation, suggesting that imines are relevant reaction intermediates.
本文描述了一种通过光氧化还原催化实现叔胺脱烷基化的温和方法的开发及其在后期官能团化中的应用。使用所开发的方法，超过 30 种不同的脂肪族、苯胺型和复杂的底物被证明可以进行脱烷基化，与文献中发现的方法相比，该方法具有更广泛的官能团耐受性。该方法的适用范围还包括具有复杂亚结构和药物底物的叔胺和仲胺分子。有趣的是，在几个环状亚结构中观察到α-氧化为亚胺，而不是脱烷基化，这表明亚胺是相关的反应中间体。
