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Direct amination of alcohols catalyzed by aluminum triflate: an experimental and computational study

Payard, Pierre?Adrien, Gu, Qingyi, Guo, Wenping, Wang, Qianran, Corbet, Matthieu, Michel, Carine, Sautet, Philippe, Grimaud, Laurence, Wischert, Raphael and Pera-Titus, Marc 2018. Direct amination of alcohols catalyzed by aluminum triflate: an experimental and computational study. Chemistry - A European Journal 24 (53) , pp. 13146-13153. 10.1002/chem.201801492

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Among the best‐performing homogeneous catalysts for the direct amination of activated secondary alcohols with electron‐poor amine derivatives, metal triflates, such as aluminum triflate, Al(OTf)3, stand out. Herein we report the extension of this reaction to electron‐rich amines and activated primary alcohols. We provide detailed insight into the structure and reactivity of the catalyst under working conditions in both nitromethane and toluene solvent, through experiment (cyclic voltammetry, conductimetry, NMR spectroscopy), and density functional theory (DFT) simulations. Competition between aniline and benzyl alcohol for Al in the two solvents explains the different reactivities. The catalyst structures predicted from the DFT calculations were validated by the experiments. Whereas a SN1‐type mechanism was found to be active in nitromethane, we propose a SN2 mechanism in toluene to rationalize the much higher selectivity observed when using this solvent. Also, unlike what is commonly assumed in homogeneous catalysis, we show that different active species may be active instead of only one.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: Wiley
ISSN: 0947-6539
Last Modified: 12 Jan 2021 15:15

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