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LiAlH 4 : From Stoichiometric Reduction to Imine Hydrogenation Catalysis
Author(s) -
Elsen Holger,
Färber Christian,
Ballmann Gerd,
Harder Sjoerd
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201803804
Subject(s) - catalysis , imine , stoichiometry , amine gas treating , chemistry , substrate (aquarium) , solvent , bar (unit) , inorganic chemistry , organic chemistry , physics , oceanography , meteorology , geology
Imine‐to‐amine conversion with catalytic instead of stoichiometric quantities of LiAlH 4 is demonstrated (85 °C, catalyst loading≥2.5 mol %, pressure≥1 bar). The effects of temperature, pressure, solvent, and catalyst modifications, as well as the substrate scope are discussed. Experimental investigations and preliminary DFT calculations suggest that the catalytically active species is generated in situ: LiAlH 4 +Ph(H)C=N t Bu→LiAlH 2 [N( t Bu)CH 2 Ph] 2 . A cooperative mechanism in which Li and Al both play a prominent role is proposed.