Theoretical investigation on the elusive biomimetic iron(Ⅲ)-iodosylarene chemistry: An unusual hydride transfer triggers the Ritter reaction  

作　　者：Lanping Gao Xiaolu Chen Dongru Sun Hua Zhao Yufen Zhao Wonwoo Nam Yong Wang 

机构地区：[1]Institute of Drug Discovery Technology,Ningbo University,Ningbo 315211,China [2]Qian Xuesen Collaborative Research Center of Astrochemistry and Space Life Sciences,Ningbo University,Ningbo 3152U,China [3]Department of Chemistry and Nano Science,Ewha Womans University,Seoul 03760,Korea

出　　处：《Chinese Chemical Letters》2021年第12期3857-3861,共5页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China (No. 21873052);the Natural Science Foundation of Zhejiang Province (No. LQ20B030004);the Ningbo Natural Science Foundation (No. 202003N4079)。

摘　　要：Introduction of iodosylarnes into biomimetic nonheme chemistry has made great achievement on identification of the subtle metal-oxygen reaction intermediates. However, after more than three decades of experimental and theoretical efforts the nature of the metal-iodosylarene adducts and the related dichotomous one-oxidant/multiple-oxident controversy have remained a matter of speculation. Herein, we report a theoretical study of the structure-activity relationship of the noted iron(Ⅲ)-iodsylarene complex,FeⅢ(Ph IO)(OTf)3(1), in oxygenation of cyclohexene. The calculated results revealed that 1 behaves like a chameleon by adapting its roles as a 2 e-oxidant or an oxygen donor, as a response to the regioselective attack of the C–H bond and the C=C bond. The oxidative C–H bond activation by 1 was found, for the first time, to proceed via a novel hydride transfer process to form a cyclohexene carbonium intermediate,such non-rebound step triggers the Ritter reaction to uptake an acetonitrile molecule to form the amide product, or proceeds with the rebound of the hydroxyl group return to the solvent cage to form the hydroxylated product. While in the C=C bond activation, 1 is a normal oxygen donor and shows two-state reactivity to present the epoxide product via a direct oxygen atom transfer mechanism. These mechanistic findings fit and explain the famous Valentine’s experiments and enrich the non-rebound scenario in bioinorganic chemistry.

关 键 词：Reaction mechanism DFT calculations Metal-iodosylbenzene Ritter reaction Olefin oxidation 

分 类 号：O621.25[理学—有机化学]