7465-86-3Relevant academic research and scientific papers
Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides
Yang, Shu-Qing,Yao, Yin-Qing,Chen, Xiao-Chao,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
, p. 1032 - 1041 (2021/05/07)
The amino dicarbonylation of aryl halides affording α-ketoamides with Pd catalysts is highly dependent on the stereoelectronic properties of the involved ligands. Ionic diphosphine ligand L4 can serve as precursor of a hemilabile P,C (phosphine, carbene)-hybrid ligand to form a stable Pd(II)-complex, Pd-L4. In contrast, analogues L1-L3 with a similar 1-(thiophen-3-yl)-benzimidazolyl skeleton behave as typical (mono/di)phosphines. The catalytic system resulting from the complexation of PdCl2(MeCN)2 and L4 exhibits good catalytic performance in terms of aryl iodides conversion (81-95%) and α-ketoamide selectivity (80-91%), as well as the available recyclability in the RTIL of [Bpy]BF4. The in situ FT-IR analysis reveals that the PdCl2(MeCN)2-L4 catalytic system favors the amino dicarbonylation toward α-ketoamides according to the proposed mechanism of cycle I, which involves two independent CO-insertion steps.
Pd-Catalyzed Oxidative Aminocarbonylation of Arylboronic Acids with Unreactive Tertiary Amines via C-N Bond Activation
Kolekar, Yuvraj A.,Bhanage, Bhalchandra M.
, p. 14028 - 14035 (2021/05/29)
An efficient synthesis of tertiary amides from aryl boronic acids and inert tertiary amines through the oxidative carbonylation via C(sp3)-N bond activation is presented. This protocol significantly restricts the homocoupling biarylketone product. It involves the use of a homogeneous PdCl2/CuI catalyst and a heterogeneous Pd/C based catalyst, which promotes C(sp3)-N bond activation of tertiary amines with aryl boronic acids. This process represents a ligand-free, base-free, and recyclable catalyst along with an ideal oxidant like molecular oxygen.
Mechanochemical Palladium-Catalyzed Carbonylative Reactions Using Mo(CO)6
van Bonn, Pit,Bolm, Carsten,Hernández, José G.
, p. 2576 - 2580 (2020/02/20)
Esters and amides were mechanochemically prepared by palladium-catalyzed carbonylative reactions of aryl iodides by using molybdenum hexacarbonyl as a convenient solid carbonyl source and avoiding a direct handling of gaseous carbon monoxide. Real-time monitoring of the mechanochemical reaction by in situ pressure sensing revealed that CO is rapidly transferred from Mo(CO)6 to the active catalytic system without significant release of molecular carbon monoxide.
Cobalt-catalyzed aminocarbonylation of (hetero)aryl halides promoted by visible light
Alexanian, Erik J.,Veatch, Alexander M.
, p. 7210 - 7213 (2020/07/23)
The catalytic aminocarbonylation of (hetero)aryl halides is widely applied in the synthesis of amides but relies heavily on the use of precious metal catalysis. Herein, we report an aminocarbonylation of (hetero)aryl halides using a simple cobalt catalyst under visible light irradiation. The reaction extends to the use of (hetero)aryl chlorides and is successful with a broad range of amine nucleophiles. Mechanistic investigations are consistent with a reaction proceeding via intermolecular charge transfer involving a donor-acceptor complex of the substrate and cobaltate catalyst.
HMF and furfural: Promising platform molecules in rhodium-catalyzed carbonylation reactions for the synthesis of furfuryl esters and tertiary amides
Qi, Xinxin,Zhou, Rong,Ai, Han-Jun,Wu, Xiao-Feng
, p. 215 - 221 (2019/11/25)
A biomass involved rhodium-catalyzed carbonylative synthesis of furfuryl esters and tertiary amides has been developed. 5-Hydroxymethylfurfural (HMF) was used as both substrate and CO surrogate for the first time in a carbonylation reaction, and both alkyl and aryl iodides were tolerated well to afford the desired furfuryl esters in moderate to good yields. In addition, furfural was also utilized as a CO source for the synthesis of tertiary amides. A variety of tertiary amides were obtained in moderate to excellent yields with good functional groups compatibility. Notably, tertiary amines were used as the amine source through a C[sbnd]N bond cleavage pathway in the absence of additional oxidant.
Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
, p. 4087 - 4101 (2019/04/30)
The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
Nickel-catalyzed reductive defunctionalization of esters in the absence of an external reductant: Activation of C-O bonds
Iyori, Yasuaki,Takahashi, Kenjiro,Yamazaki, Ken,Ano, Yusuke,Chatani, Naoto
supporting information, p. 13610 - 13613 (2019/11/14)
The nickel-catalyzed reductive cleavage of esters in the absence of an external reductant, which involves the cleavage of an inert acyl C-O bond in O-Alkyl esters is reported. Various groups, such as N-containing heterocycles, esters, amides, and even arene rings can function as a directing group.
Tert -Butyl nitrite promoted transamidation of secondary amides under metal and catalyst free conditions
Sureshbabu, Popuri,Azeez, Sadaf,Chaudhary, Priyanka,Kandasamy, Jeyakumar
, p. 845 - 850 (2019/01/30)
A mild and efficient method is demonstrated for the transamidation of secondary amides with various amines including primary, secondary, cyclic and acyclic amines in the presence of tert-butyl nitrite. The reaction proceeds through the N-nitrosamide intermediate and provides the transamidation products in good to excellent yields at room temperature. Moreover, the developed methodology does not require any catalyst or additives.
Versatile Heterogeneous Palladium Catalysts for Diverse Carbonylation Reactions under Atmospheric Carbon Monoxide Pressure
Vico Solano, Marta,González Miera, Greco,Pascanu, Vlad,Inge, A. Ken,Martín-Matute, Belén
, p. 1089 - 1095 (2018/02/06)
Herein, we report a versatile carbonylation protocol using heterogeneous Pd0 nanoparticles supported on the metal–organic frameworks (MOFs) MIL-88B-NH2 (Fe/Cr). The synthesis of a vast array of carbonyls, which includes amides, esters, carboxylic acids, and α-ketoamides, was achieved through mono- and dicarbonylation reactions. The selectivity could be controlled simply by tuning the reaction conditions. Superior activity and selectivity were recorded in some cases compared to that achieved with commercial Pd/C. However, the utility of an elaborate catalyst support is questionable and important reactivity and recyclability issues are discussed.
Alternative formation of amides and β-enaminones from aroyl chlorides using the TiCl4-trialkylamine reagent system
Leggio, Antonella,Comandè, Alessandra,Belsito, Emilia Lucia,Greco, Marianna,Lo Feudo, Lucia,Liguori, Angelo
, p. 5677 - 5683 (2018/08/17)
The TiCl4/NR3 reagent system has been successfully employed for the synthesis of amides and β-enaminones. The reaction of variously substituted benzoyl chlorides with the TiCl4/NR3 reagent system, by using two different experimental procedures (Method A and Method B), afforded alternatively the corresponding amides and β-enaminones as unique or major products. The two developed protocols were investigated with a series of tertiary amines. The reactions, modulated by the presence of TiCl4, provided the corresponding amides or β-enaminones with satisfactory yields. This paper reports a new method for carbon-carbon bond formation via the reaction of aroyl chlorides with the TiCl4/NR3 reagent system.
