Rhenium‐Catalyzed Oxidative Cyanation of Tertiary Amines with TMSCN

Abstract

Oxidative cyanation of sp3 C–H bonds at the α position of tertiary amines by using TMSCN as the cyanide donor and a novel high‐valent rhenium(V) complex was developed. The reaction offers the corresponding α‐aminonitriles in good yields with tert‐butyl hydroperoxide as the oxidant under mild and acid‐free reaction conditions.

PEGylated magnetic nanoparticles (PEG@Fe 3 O 4 ) as cost effective alternative for oxidative cyanation of tertiary amines via C H activation

“…Further, these bi-functional organic compounds having adjacent functional groups show dual reactivity as the nucleophilic addition provides an easy access to various compounds such as ␣-amino aldehydes, ketones and ␤-amino alcohols [20][21][22][23][24][25]. So far a number of metal-based catalysts, such as Fe [26][27][28], Ru [29,30], V [31], Mo [32], Au [33] and Re [34] in the presence of oxidants such as molecular oxygen, hydrogen peroxide, tert-butyl hydroperoxide (TBHP) have been reported for the direct oxidative cyanation of tertiary amines. Photoredox catalysts mainly based on ruthenium have also been reported for the oxidative ␣-cyanation of sp 3 C H bonds of tertiary amines [35][36][37][38].…”

New trends and applications in cyanation isotope chemistry

“…The formation of α‐cyanoamines 51 by oxidative cyanations of C―H bonds has been intensively studied in recent years . Several different protocols applying stoichiometric amounts of TMSCN under very mild (room temperature) and acid free conditions have been reported: (1) FeCl 2 , tert‐butyl hydroperoxide (TBHP), MeOH, rt (scheme ); (2) Au(bipyridyl)Cl 2 , 2 eq.…”

Synthesis of α-aminonitriles via a FeSO4-mediated oxidative cyanation of tertiary amines with benzoyl cyanide and molecular oxygen or TBHP

“…21 Afterwards, in order to have high efficiency, high yield, and safe operation, several catalyst systems based on various transition metals were disclosed, including V 2 O 5 , 22 FeCl 2 , 23 polymer supported iron(II) phthalocyanines, 24 iron oligopyridine complexes, 25 goldcomplex, 26 and rhenium-complex. 27 However, these transition metal-catalyzed reactions all lead to by-product formation. Taking N,N-dimethylaniline as an example, its oxidation could produce N-methylformanilide 15 and N-methylaniline, 25,28 both of them derived from the oxidation of tertiary amine.…”