41681-72-5Relevant articles and documents
Zinc-catalyzed reduction of amides: Unprecedented selectivity and functional group tolerance
Das, Shoubhik,Addis, Daniele,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
, p. 1770 - 1771 (2010)
(Chemical Equation Presented) A novel zinc-catalyzed reduction of tertiary amides was developed. This system shows remarkable chemoselectivity and substrate scope tolerating ester, ether, nitro, cyano, azo, and keto substituents. Copyright
Development and mechanistic investigation of a highly efficient iridium(V) silyl complex for the reduction of tertiary amides to amines
Park, Sehoon,Brookhart, Maurice
experimental part, p. 640 - 653 (2012/03/13)
The cationic Ir(III) acetone complex (POCOP)Ir(H)2(acetone) + (POCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) was shown to catalyze the reduction of a variety of tertiary amides to amines using diethylsilane as reductant. Mechanistic studies established that a minor species generated in the reaction, the neutral silyl trihydride Ir(V) complex (POCOP)IrH3(SiEt2H), was the catalytically active species. High concentrations of this species could be conveniently generated by treatment of readily available (POCOP)IrHCl with tert-butoxide in the presence of Et2SiH2 under H2. Thus, using this mixture in the presence of a trialkylammonium salt, a wide array of tertiary amides, including extremely bulky substrates, are rapidly and quantitatively reduced to tertiary amines under mild conditions with low catalyst loading. A detailed mechanistic study has been carried out and intermediates identified. In brief, (POCOP)IrH3(SiEt2H) reduces the amide to the hemiaminal silyl ether that, in the presence of a trialkylammonium salt, is ionized to the iminium ion, which is then reduced to the tertiary amine by Et 2SiH2. Good functional group compatibility is demonstrated, and a high catalyst stability has provided turnover numbers as high as 10 000.
