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Pyridylidene‐Mediated Dihydrogen Activation Coupled with Catalytic Imine Reduction
Author(s) -
Auth Johanna,
Padevet Jaroslav,
Mauleón Pablo,
Pfaltz Andreas
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201503233
Subject(s) - pyridinium , chemistry , imine , electrophile , trifluoromethanesulfonate , medicinal chemistry , catalysis , ketone , hydride , amine gas treating , organic base , hydrogen , combinatorial chemistry , photochemistry , organic chemistry
In recent years, dihydrogen activation at non‐metallic centers has received increasing attention. A system in which dihydrogen is trapped by a pyridylidene intermediate that is generated from a pyridinium salt and a base is now reported. The dihydropyridine formed in this process can act as reducing agent towards organic electrophiles. By coupling the hydrogen‐activation step with subsequent hydride transfer from the dihydropyridine to an imine, a catalytic process was established. Treatment of the N ‐phenylimine of phenyl trifluoromethyl ketone with 5–20 mol % of N‐ mesityl‐3,5‐bis(2,6‐dimethylphenyl)pyridinium triflate and 0.3–1.0 equivalents of LiN(SiMe 3 ) 2 under 50 bar of hydrogen gas resulted in high conversion into the corresponding amine.