Theoretical investigation on the elusive biomimetic iron(III)-iodosylarene chemistry: An unusual hydride transfer triggers the Ritter reaction
- 주제(키워드) Reaction mechanism , DFT calculations , Metal-iodosylbenzene , Ritter reaction , Olefin oxidation
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Gao, Lanping; Chen, Xiaolu; Sun, Dongru; Zhao, Hua; Zhao, Yufen; Nam, Wonwoo; Wang, Yong] Ningbo Univ, Inst Drug Discovery Technol, Ningbo 315211, Peoples R China; [Gao, Lanping; Chen, Xiaolu; Sun, Dongru; Zhao, Hua; Zhao, Yufen; Wang, Yong] Ningbo Univ, Qian Xuesen Collaborat Res Ctr Astrochem & Space, Ningbo 315211, Peoples R China; [Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
- 등재 SCIE, SCOPUS
- 발행기관 ELSEVIER SCIENCE INC
- 발행년도 2021
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000191181
- 본문언어 영어
- Published As https://doi.org/10.1016/j.cclet.2021.05.030
초록/요약
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 (PhIO)(OTf)(3) (1), in oxygenation of cyclohexene. The calculated results revealed that 1 behaves like a chameleon by adapting its roles as a 2e-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. (C) 2021 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
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