BROWSE

Related Scientist

pradhan,sourav's photo.

pradhan,sourav
분자활성촉매반응연구단
more info

ITEM VIEW & DOWNLOAD

A Formal γ-C-H Functionalization of Carboxylic Acids Guided by Metal-Nitrenoids as an Unprecedented Mechanistic Motif

Cited 0 time in webofscience Cited 0 time in scopus
45 Viewed 0 Downloaded
Title
A Formal γ-C-H Functionalization of Carboxylic Acids Guided by Metal-Nitrenoids as an Unprecedented Mechanistic Motif
Author(s)
Sourav Pradhan; Jeonguk Kweon; Manoj Kumar Sahoo; Hoimin Jung; Joon Heo; Yeong Bum Kim; Dongwook Kim; Jung-Woo Park; Sukbok Chang
Publication Date
2023-12
Journal
Journal of the American Chemical Society, v.145, no.51, pp.28251 - 28263
Publisher
American Chemical Society
Abstract
Harnessing the key intermediates in metal-catalyzed reactions is one of the most essential strategies in the development of selective organic transformations. The nitrogen group transfer reactivity of metal-nitrenoids to ubiquitous C-H bonds allows for diverse C-N bond formation to furnish synthetically valuable aminated products. In this study, we present an unprecedented reactivity of iridium and ruthenium nitrenoids to generate remote carbocation intermediates, which subsequently undergo nucleophile incorporation, thus developing a formal gamma-C-H functionalization of carboxylic acids. Mechanistic investigations elucidated a unique singlet metal-nitrenoid reactivity to initiate an abstraction of gamma-hydride to form the carbocation intermediate that eventually reacts with a broad range of carbon, nitrogen, and oxygen nucleophiles, as well as biorelevant molecules. Alternatively, the same intermediate can lead to deprotonation to afford beta,gamma-unsaturated amides in a less nucleophilic solvent.
URI
https://pr.ibs.re.kr/handle/8788114/14768
DOI
10.1021/jacs.3c11628
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
Files in This Item:
There are no files associated with this item.

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