Heterobimetallic Lanthanide–Sodium Alkoxides Catalyze the Amidation of Esters

Abstract

Heterobimetallic lanthanide-sodium alkoxides Ln 2 Na 8 (OCH 2 CF 3 ) 14 (THF) 6 catalyzed the reaction of esters and amines to produce amides in up to 99 %y ields. They showed high catalytic activity for aw ide scope of substrates under solvent-free conditions. The cooperation of lanthanum and sodium alkoxide is proposed to accountf or the good activity.

Recent developments in catalytic amide bond formation

“…La(OTf) 3 has also been used to amidate alkyl and aryl (including heteroaryl) ethyl esters with secondary alkyl amines at 70 C. [126] Both examples are noteworthy for heating. [128] Other metals capable of acting as Lewis acid catalysts for amidation include calcium, which could amidate methyl esters at 110 C F I G U R E 1 6 Group V metal catalyzed methyl ester amidation assisted by bidentate chelation. R = Alkyl in toluene with a variety of alkyl amines and could function at room temperature for select examples.…”

“…Methyl Luo [127] La 2 Na 8 (OCH 2 CF 3 ) 14 (THF) 6 Neat 80 .5 Methyl Yao [128] Nb(OEt) 5 Neat 50-80 2-5 Methyl Yamamoto [120] Nb 2 O 5 Neat 140 50* Methyl Shimizu [119] Ni(cod) 2 Lx Toluene 60 15 Methyl Garg [23] Ni(cod) 2 Lx Toluene 140 10 Methyl Newman [115,116] Ni(Glyme)Cl 2 Lx NMP 120 7.5 Methyl Hu [117] Nitroarenes as amine source Pd(IPr)(allyl)Cl Toluene 110 3 Phenyl Newman [118] Ta(OEt) 5 Toluene 60-100 10 Methyl Yamamoto [122] Ta(OMe) 5 Neat or CHCl 3 or DMSO 40-70 10 Methyl Yamamoto [121] Use of TMSIM as additive lowers temp to 30-50 ZrCl 4 Toluene 90 5 Methyl Ghinet [123] ZrCp 2 Cl 2 Toluene 110 10 Methyl Mecinovic [124] 4.2.1 | Acceptorless oxidative amidation…”

Towards the Development of Frustrated Lewis Pair (FLP) Catalyzed Hydrogenations of Tertiary and Secondary Carboxylic Amides

“…[SI7] N,N'-(hexane-1,6-diyl)dibenzamide (16e) white powder, 84% (2.74 g, 8.45 mmol) The NMR data is in agreement with literature reported chemical shifts and signal pattern. [SI8] Accepted Manuscript…”

Iodine-Promoted N-Acylation of Amines with Hydrazide: An Efficient Metal-Free Amidation

“…. 22 Compound 3k was and purified by column chromatography (5:1 PE/EtOAc), obtained as a yellow solid (76.4 mg, 72%), m.p. 72-73 °C.…”

“…N,N'-(hexane-1,6-diyl)dibenzamide (3u). 28 Compound 3u was purified by column chromatography (3:1 PE/EtOAc), obtained as a white solid (105.4 mg, 65%), m.p. 151-153 °C.…”