Oxidatively Induced Reductive Elimination: Exploring the Scope and Catalyst Systems with Ir, Rh, and Ru Complexes

Cited 0 time in webofscience Cited 0 time in scopus
14 Viewed 6 Downloaded
Title
Oxidatively Induced Reductive Elimination: Exploring the Scope and Catalyst Systems with Ir, Rh, and Ru Complexes
Author(s)
Jinwoo Kim; Kwangmin Shin; Seongho Jin; Dongwook Kim; Sukbok Chang
Publication Date
2019-03
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.141, no.9, pp.4137 - 4146
Publisher
AMER CHEMICAL SOC
Abstract
Direct conversion of C-H bonds into C-C bonds is a promising alternative to the conventional cross-coupling reactions, thus giving rise to a wide range of efficient catalytic C-H functionalization reactions. Among the elementary stages in the catalytic C-C bond formation, reductive elimination constitutes a key step of the catalytic cycle, and, therefore, extensive studies have been made to facilitate this process. In this regard, oxidation on the metal center of a post-transmetalation intermediate would be an appealing approach. Herein, we have explored the substrate scope, catalyst systems, and oxidation tools to prove that the oxidatively induced reductive elimination (ORE) plays a critical role in the product-releasing C-C bond formation. Notably, we have demonstrated that ORE broadly operates with a series of half-sandwich d 6 Ir(III)-, Rh(III)-, and Ru(II)-aryl complexes. We have described that the metal center oxidation of the isolable post-transmetalation intermediates by means of chemical-or electro-oxidation can readily deliver the desired arylated products upon reductive elimination even at ambient temperature. Computational studies delineated the thermodynamics of the reductive elimination, where the activation barriers are shown to be significantly reduced upon increasing the oxidation states of the intermediates. We were also successful in corroborating this ORE in the corresponding Rh-methyl complex. In addition, catalytic conditions were optimized to incorporate this mechanistic understanding into the Ir-, Rh-, and Ru-catalyzed C-C bond formations under mild conditions. © Copyright 2019 American Chemical Society
URI
https://pr.ibs.re.kr/handle/8788114/5674
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
jacs.9b00364.pdfDownload

qrcode

  • facebook

    twitter

  • Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.
해당 아이템을 이메일로 공유하기 원하시면 인증을 거치시기 바랍니다.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse