Palladium‐Catalyzed Aminocarbonylation of Aryl Chlorides at Atmospheric Pressure: The Dual Role of Sodium Phenoxide

Abstract

Kein Druck, kein Stress: Ein allgemein anwendbares, mildes System für die Pd‐katalysierte Carbonylierng von Arylchloriden zu den entsprechenden Amiden wurde entwickelt. Der Katalysator enthält einen einfachen, luftstabilen und kommerziell erhältlichen Liganden und arbeitet bei 1 atm CO‐Druck (siehe Schema, Cy=Cyclohexyl). Entscheidend ist der Zusatz von Natriumphenoxid, dessen Rolle durch In‐situ‐IR‐Spektroskopie untersucht wurde.

Direct Oxidative Amidation between N,N‐dimethylanilines and Anhydrides Using Metal‐Organic Framework [Cu2(EDB)2(BPY)] as an Efficient Heterogeneous Catalyst

“…[1,7,8] Notably, tertiary amines are commonly present in various natural products, and more easily available than secondary amines. [2,9,10] Recently, Li and co-workers reported a new and efficient method for direct amide formation by the reaction of tertiary amines with aldehydes. [2,9,10] Recently, Li and co-workers reported a new and efficient method for direct amide formation by the reaction of tertiary amines with aldehydes.…”

“…[7,8] Indeed, several synthetic routes were investigated for amide formation from many starting material sources. [2,9,10] Recently, Li and co-workers reported a new and efficient method for direct amide formation by the reaction of tertiary amines with aldehydes. [8] To avoid the disadvantages associated with the aldehydes, the approach was subsequently improved to access direct oxidative amidation transformation between tertiary amines and anhydrides as acylation reagents in the presence of FeCl 2 as catalyst.…”

Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

“…[5] In the last few decades,transition-metal-catalyzed carbonylation of aryl halides and related compounds with carbon monoxide (CO) and amines via aryl-metal species has rapidly evolved to have tremendous impact since the pioneering work of Heck and co-workers in 1974 (Scheme 1b). [6] Since then, many excellent works have been achieved by the groups of Beller, [7] Buchwald, [8] Jiao, [9] Li, [10] and others. [11] This strategy has become ap owerful tool to synthesize amides,o wing to the unique ability of CO serving as an excellent carbonyl source.B ut the current methods are reaching their inherent limits,a nd it is necessary to develop new methods for amide synthesis.…”

“…We started our research by investigating C À Ha midation of N-methylindole (1a)w ith CO (balloon pressure) and 4toluenesulfonyl azide (2a)i nt he presence of various metal catalysts.T oo ur delight, the desired amidation product 3a was obtained in 20 %y ield with 5mol %C o 2 (CO) 8 as the catalyst in MeCN at 80 8 8C( Table 1, entry 1). Tr ace amounts of product could be detected with other metal catalysts,such as Fe 2 Cp 2 (CO) 4 ,N i(cod) 2 ,a nd Cu(OAc) 2 (entries 2-4).…”

Highly Efficient Amide Synthesis from Alcohols and Amines by Virtue of a Water‐Soluble Gold/DNA Catalyst

“…Generally, the traditional syntheses of amides are limited by toxicity issues and the harsh conditions employed. Alternative methods,2 such as the Beckmann rearrangement,3a,b Staudinger reaction,3c,d aminocarbonylation of aryl halides,3e–h hydration of the nitriles,3i oxidation of the terminal alkynes,3j,k and ligation of α‐halo nitroalkanes with amines3l have emerged to improve the preparation of amides. Recently, amidation of aldehydes with amines under the catalysis of metal complexes was reported 4.…”