fast copper-catalyzed aryl c(sp2)-h amination with n-(2-pyridyl)sulfonyl directing group at ambient temperature

Open Access
Author:
Ai, Zhaoyan
Graduate Program:
Chemistry
Degree:
Master of Science
Document Type:
Master Thesis
Date of Defense:
March 26, 2014
Committee Members:
  • Gong Chen, Thesis Advisor
Keywords:
  • c-h activation
  • cu catalysis
  • aryl amination
  • room temperature
Abstract:
The ubiquity of aryl amines makes them a crucial part in various organic syntheses. An immense effort has been made, therefore, to develop efficient methods to synthesize them. Traditionally, nitration, alkylation and reduction are applied to arenes and derivatives to enable such transformation, which is now often replaced by their counterparts utilizing palladium, nickel and copper catalysis. The rapidly developing field of C-H functionalization has also provided new insights into this topic. This research describes a new method for the synthesis of aryl amines utilizing a cheap copper catalyst copper(II) chloride and an auxiliary agent, magnesium chloride, under the direction of an N-(2-pyridyl)sulfonyl group. A thorough and systematic study has been conducted to optimize the reaction yield by changing different aspects of reaction conditions including catalyst, oxidant, solvent, temperature, stoichiometry etc. The optimized conditions allow the reaction to occur at room temperature in 15 min with moderate to good yields. The scope of this reaction as well as a preliminary investigation into the reaction mechanism is also described in this work. While the optimal conditions were determined, the details of mechanism still remain unclear. Possible mechanistic pathways and potential experiments that could help identify the mechanism are proposed in the third chapter.