Key Laboratory of Molecular Recognition and Function, Institute of Chemistry , The Chinese Academy of Sciences and University of Chinese Academy of Sciences , Beijing 100049 , China.
Center of Basic Molecular Science (CBMS), Department of Chemistry , Tsinghua University , Beijing 100084 , China.
J Org Chem. 2019 Mar 1;84(5):2542-2555. doi: 10.1021/acs.joc.8b02948. Epub 2019 Feb 19.
We report herein our mechanistic studies of the ortho-quinone-catalyzed aerobic oxidation of primary, secondary, and tertiary amines. Two different catalytic pathways were discovered for the reductive half reactions: for primary amines, the reaction was found to proceed via a transamination pathway, while the reactions with secondary amines and tertiary amines proceeded via hydride transfer. We also found that the amine substrates could significantly promote the regeneration of the ortho-quinone catalyst in the oxidative half reaction, in which a proton transfer occurs between the amine substrates and catechol derivatives (the reduced form of the ortho-quinone catalyst).
我们在此报告了邻醌催化的伯、仲、叔胺的有氧氧化的机理研究。我们发现还原半反应有两种不同的催化途径：对于伯胺，反应是通过转氨途径进行的，而仲胺和叔胺的反应则是通过氢化物转移进行的。我们还发现，在氧化半反应中，胺底物可以显著促进邻醌催化剂的再生，其中胺底物和儿茶酚衍生物（邻醌催化剂的还原形式）之间发生质子转移。
