Improved Synthesis of Diarylamines and Aryl Alkyl Ethers

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  • Published: 31 July 2018
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
  • Source / Publisher: Organic Letters/ACS Publications
  • Associated Societies: American Chemical Society (ACS), USA
thumbnail image: Improved Synthesis of Diarylamines and Aryl Alkyl Ethers

Diarylamines are commonly used, e.g, in dyes. There is a range of transition-metal-catalyzed syntheses for this type of compound, starting from aryl halides or boronic acids. Transition-metal-free reactions starting from other aryl derivatives, such as thioethers, would be useful to complement the existing synthetic pathways.

Wanxiang Zhao, Xue-Qiang Wang, Hunan University, Changsha, China, and colleagues have developed a transition-metal-free synthesis of diarylamines under mild conditions. The team used nitrile-substituted aryl alkyl thioethers (pictured) as starting materials and reacted them with aniline nucleophiles using KHDMS (potassium hexamethyldisilazane) as a base, and 1,4-dioxane as the solvent at 60 °C to give the desired diarylamines in good yields. The protocol can also be used to synthesize aryl alkyl ethers by replacing the anilines with alcohols and KHDMS with KOtBu (potassium tert-butoxide), as well as raising the reaction temperature to 80 °C.

The reactions have a broad substrate scope and tolerate a variety of functional groups. The researchers propose a nucleophilic aromatic substitution as the reaction mechanism. The team was able to perform the reaction on a gram scale. The nitrile group allows the products to be transformed further into useful chemical building blocks.


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