A General Approach to Site‐Specific, Intramolecular C−H Functionalization Using Dithiocarbamates
作者:Christina G. Na、Erik J. Alexanian
DOI:10.1002/anie.201806963
日期:2018.10
Intramolecularhydrogen atom transfer is an established approach for the site‐specific functionalization of unactivated, aliphatic C−H bonds. Transformations using this strategy typically require unstable intermediates formed using strong oxidants and have mainly targeted C−H halogenations or intramolecular aminations. Herein, we report a site‐specific C−H functionalization that significantly increases
[Cp*RhCl2]2-catalyzed ortho-C–H bond amination of acetophenone o-methyloximes with primary N-chloroalkylamines: convenient synthesis of N-alkyl-2-acylanilines
作者:Ka-Ho Ng、Zhongyuan Zhou、Wing-Yiu Yu
DOI:10.1039/c3cc42937g
日期:——
Rh(III)-catalyzed aromatic CâH amination of acetophenone o-methyloximes with primary N-chloroalkylamines was developed, and the arylamine products were obtained in up to 92% yield. The reaction probably involves rate-limiting electrophilic CâH bond cleavage (kH/kD = 2).
We carried out a kinetic study of the reaction between iodide ion and various primary N-chloramines and found it to be first-order in the latter. Experiments also showed the rate constant for the reaction to be directly proportional to the iodide and hydrogen ion concentrations. The influence of the buffer concentration reveals the presence of general acid catalysis processes. (C) 1996 John Wiley & Sons. Inc.
Ferriol, Michel; Gazet, Josette; Saugier-Cohen Adad, Marie-Therese, Journal de Chimie Physique et de Physico-Chimie Biologique, 1989, vol. 86, # 9, p. 1955 - 1978