A commercial cyclopentadienylrutenium
dicarbonyl dimer ([CpRu(CO)2]2) efficiently
catalyzes the formation of N–H
imines and carbonyl compounds simultaneously from β-hydroxy
azides via C–C bond cleavage under visible light. Density functional
theory calculations for the cleavage reaction support the mechanism
involving chelation of alkoxy azide species and liberation of nitrogen
as the driving force. The synthetic utility of the reaction was demonstrated
by a new amine synthesis promoted by chemoselective allylation of
imine and synthesis of isoquinoline.
A new method for the synthesis of N−H imines from αazidocarboxylic acids was developed, which proceeds through decarboxylative C−C bond cleavage catalyzed by a commercial diruthenium complex ([CpRu(CO) 2 ] 2 ) under visible light irradiation at room temperature within several minutes. The reactive products undergo condensation, which forms cyclic trimers (2,4,6-trialkylhexahydro-1,3,5-triazines) or linear N,N′-bis-(arylmethylidene)arylmethanediamines in quantitative yields. Alternatively, the N−H imines can be trapped with benzylamine and 2-(aminomethyl)aniline, providing stable N-benylimines and tetrahydroquinazolines, respectively. Subsequent oxidation of tetrahydroquinazolines produced quinazolines.
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