Mechanistic studies on the Rh(III)-mediated amido transfer process leading to robust C-H amination with a new type of amidating reagent

Journal of the American Chemical Society
Yoonsu ParkSukbok Chang

Abstract

Mechanistic investigations on the Cp*Rh(III)-catalyzed direct C-H amination reaction led us to reveal the new utility of 1,4,2-dioxazol-5-one and its derivatives as highly efficient amino sources. Stepwise analysis on the C-N bond-forming process showed that competitive binding of rhodium metal center to amidating reagent or substrate is closely related to the reaction efficiency. In this line, 1,4,2-dioxazol-5-ones were observed to have a strong affinity to the cationic Rh(III) giving rise to dramatically improved amidation efficiency when compared to azides. Kinetics and computational studies suggested that the high amidating reactivity of 1,4,2-dioxazol-5-one can also be attributed to the low activation energy of an imido-insertion process in addition to the high coordination ability. While the characterization of a cationic Cp*Rh(III) complex bearing an amidating reagent was achieved, its facile conversion to an amido-inserted rhodacycle allowed for a clear picture on the C-H amidation process. The newly developed amidating reagent of 1,4,2-dioxazol-5-ones was applicable to a broad range of substrates with high functional group tolerance, releasing carbon dioxide as a single byproduct. Additional attractive features of this...Continue Reading

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Citations

Jun 14, 2016·The Journal of Organic Chemistry·Ebrahim KianmehrKhalid Mohammed Khan
Sep 10, 2016·Science·Mahesh P PaudyalJohn R Falck
Nov 5, 2016·The Journal of Organic Chemistry·Lanting XuDawei Ma
Sep 2, 2016·Journal of the American Chemical Society·Weilong XieSukbok Chang
Oct 6, 2016·Organic Letters·Xiaolong YuJin Zhu
Jan 5, 2017·Chemical Reviews·Yoonsu ParkSukbok Chang
Apr 20, 2017·Organic & Biomolecular Chemistry·Gongutri BorahPitambar Patel
Apr 19, 2017·Journal of the American Chemical Society·Xiaoming WangFrank Glorius
Mar 16, 2017·Angewandte Chemie·Juhyeon ParkSukbok Chang
May 14, 2017·Angewandte Chemie·Huai-Wei WangJin-Quan Yu
Jun 3, 2016·Chemistry : a European Journal·Ying ChengCarsten Bolm
Jun 4, 2016·Chemistry : a European Journal·Conghui TangNing Jiao
May 31, 2017·Chemistry : a European Journal·Yeongyu HwangSukbok Chang
Apr 14, 2016·Chemical Society Reviews·T GenschJ Wencel-Delord
Jul 24, 2018·Chemical Society Reviews·Carlo SambiagioMichael Schnürch
Jul 10, 2018·Angewandte Chemie·Jesús Sanjosé-OrdunaMónica H Pérez-Temprano
Oct 29, 2017·Angewandte Chemie·Peng Wen TanJayasree Seayad
Jun 7, 2018·Angewandte Chemie·Wusheng GuoArjan W Kleij

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