Aminolysis of Aryl Ester Using Tertiary Amine as Amino Donor via C–O and C–N Bond Activations

Abstract

An aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of a broad scope of tertiary amides under neutral and mild conditions. The mechanism may undergo the two key steps of oxidative addition of acyl C-O bond in parent ester and C-N bond cleavage of tertiary amine via an iminium-type intermediate.

Transition-metal catalysed C–N bond activation

“…Based on the same oxidative C-N bond activation method, a Pd(OAc) 2 -catalysed aminolysis reaction of aryl esters with inert tertiary amines was developed by Bao and co-workers. 36 A variety of amines including trialkyl, N, N-dialkylaniline and heterocyclic amines could smoothly react with various carboxylic esters to produce the desired amides in 51−91% yields (Scheme 39).…”

Solvent- and transition metal-free amide synthesis from phenyl esters and aryl amines

“…9,[16][17][18][19] Amide synthesis from amines and cheap unactivated esters using various catalysts is rather promising. [20][21][22][23][24][25][26] Recent publications have documented rapid transformation of Buchwald-Hartwig cross-coupling into an efficient tool to create C-N bonds from aryl halides and amines used abundantly in industrial ne organic synthesis. [27][28][29][30][31] In the past two years, efforts of groups lead by Stephen G. Newman (Scheme 1A), 32 Michal Szostak (Scheme 1B), 33 and Nilay Hazari (Scheme 1C) 34 resulted in a successful transfer of aryl halide cross-coupling techniques onto esters.…”

Microwave-promoted direct amidation of unactivated esters catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions

“…Great efforts have recently been made to avoid this problem by using activating reagents or catalysts. 9-21 Efficient catalytic systems based on inorganic catalysts (K 3 PO 4 , 9 NaOMe, 10 Mg(OCH 3 ) 2 or CaCl 2 , 11 and Mg 3 N 2 12 ), organic catalysts (tertbutylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP), 13 1,5, 7-triazabicyclo[4.4.0]dec-5-ene (TBD), 14 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 15 and N-heterocyclic carbine 16 ), metallic catalysts (Ru-MACHO, 17 La(OTf) 3 , 18 Pd(OAc) 2 , 19 and DABCO(AlMe 3 ) 2 20 ), and enzymatic-catalyzed transformations 21 have been reported. However, some of these methods still suffer from certain demerits, such as recycle of catalysts, limited substrate scopes, low selectivities, and long reaction times.…”