105973-44-2

Upstream product

• 127-19-5 N,N-dimethyl acetamide 
• 89-95-2 2-methyl-benzyl alcohol 
• 201230-82-2 carbon monoxide 
• 611-15-4 1-methyl-2-vinyl-benzene 
• 68-12-2 N,N-dimethyl-formamide 
• 95-49-8 2-methylchlorobenzene 

Relevant academic research and scientific papers

Iridium-catalyzed selective α-alkylation of unactivated amides with primary alcohols

The first α-alkylation of unactivated amides with primary alcohols is described. An effective and robust iridium pincer complex has been developed for selective α-alkylation of tertiary and secondary acetamides involving a borrowing hydrogen methodology. The method is compatible with alcohols bearing various functional groups. This presents a convenient and environmentally benign protocol for α-alkylation of amides.

Nickel-catalyzed: C-alkylation of thioamide, amides and esters by primary alcohols through a hydrogen autotransfer strategy

A simple catalyst of Ni(OAc)2 and P(t-Bu)3 enables selective C-alkylation of thioacetamides and primary acetamides with alcohols for the first time. Monoalkylation of thioamides, amides and t-butyl esters occurs in excellent yields (>95%). Mechanistic studies reveal that the reaction proceeds via a hydrogen autotransfer pathway. This journal is

Radical condensation between benzylic alcohols and acetamides to form 3-arylpropanamides

A new radical condensation reaction is developed where benzylic alcohols and acetamides are coupled to generate 3-arylpropanamides with water as the only byproduct. The transformation is performed with potassium tert-butoxide as the only additive and gives rise to a variety of 3-arylpropanamides in good yields. The mechanism has been investigated experimentally with labelled substrates, trapping experiments and spectroscopic measurements. The findings indicate a radical pathway where potassium tert-butoxide is believed to serve a dual role as both base and radical initiator. The radical anion of the benzylic alcohol is proposed as the key intermediate, which undergoes coupling with the enolate of the amide to form the new C-C bond. Subsequent elimination to the corresponding cinnamamide and olefin reduction then affords the 3-arylpropanamides.

Bidentate Ru(II)-NC Complexes as Catalysts for α-Alkylation of Unactivated Amides and Esters

Five Ru(II)-NC complexes were tested as catalysts for α-alkylation of unactivated amides using alcohols as alkylating agents, and complex {(C5H4N)-(C6H4)}RuCl(CO)(PPh3)2 (1) showed the highest activity. With 0.5 mol% catalyst loading, a series of α-alkylated amides were isolated at 80 °C within 6 hours. Furthermore, under similar conditions, complex 1 was also active for α-alkylation of unactivated esters with alcohols, and the reaction time was shortened to 1.5 hours. The catalytic performance of 1 is comparable to the best reported catalyst.

Manganese-catalyzed direct C-C coupling of α-C-H bonds of amides and esters with alcohols: Via hydrogen autotransfer

Herein we report an efficient manganese-catalyzed C-alkylation of unactivated amides and tert-butyl acetate using alcohols as alkylating agents. This elegant approach exhibits a broad substrate scope providing the C-C coupled products of amides via a hydrogen auto-transfer strategy using aryl, heteroaryl, and aliphatic alcohols.

Ni-Catalyzed Α-Alkylation of Unactivated Amides and Esters with Alcohols by Hydrogen Auto-Transfer Strategy

A transition-metal-catalyzed borrowing hydrogen/hydrogen auto-transfer strategy allows the utilization of feedstock alcohols as an alkylating partner, which avoids the formation of stoichiometric salt waste and enables a direct and benign approach for the construction of C-N and C?C bonds. In this study, a nickel-catalyzed α-alkylation of unactivated amides and ester (tert-butyl acetate) is carried out by using primary alcohols under mild conditions. This C?C bond-forming reaction is catalyzed by a new, molecularly defined nickel(II) NNN-pincer complex (0.1–1 mol %) and proceeds through hydrogen auto-transfer, thereby releasing water as the sole byproduct. In addition, N-alkylation of cyclic amides under Ni-catalytic conditions is demonstrated.

Palladium-Catalyzed Hydrocarbonylative C-N Coupling of Alkenes with Amides

An efficient palladium-catalyzed hydrocarbonylative C-N coupling of alkenes with amides has been developed. The reaction was performed via hydrocarbonylation of alkenes, followed by acyl metathesis with amides. Both intermolecular and intramolecular react

A highly efficient catalytic α-alkylation of unactivated amides using primary alcohols

The α-alkylation of unactivated amides with alcohols is described. Using a NCP-type pincer Ir complex as the precatalyst and KOtBu as the base, the reactions of secondary or tertiary acetamides with benzyl or nonbenzyl primary alcohols occur at 80 °C, furnishing the alkylation products in good yields. This method represents a practical and green means of α-alkylation of amides in a relatively mild, efficient, and selective manner with low catalyst loadings (0.5 mol %).

General and Mild Cobalt-Catalyzed C-Alkylation of Unactivated Amides and Esters with Alcohols

The borrowing hydrogen or hydrogen autotransfer methodology is an elegant and sustainable or green concept to construct carbon-carbon bonds. In this concept, alcohols, which can be obtained from barely used and indigestible biomass, such as lignocellulose, are employed as alkylating reagents. An especially challenging alkylation is that of unactivated esters and amides. Only noble metal catalysts based on iridium and ruthenium have been used to accomplish these reactions. Herein, we report on the first base metal-catalyzed α-alkylation of unactivated amides and esters by alcohols. Cobalt complexes stabilized with pincer ligands, recently developed in our laboratory, catalyze these reactions very efficiently. The precatalysts can be synthesized easily from commercially available starting materials on a multigram scale and are self-activating under the basic reaction conditions. This Co catalyst class is also able to mediate alkylation reactions of both esters and amides. In addition, we apply the methodology to synthesize ketones and to convert alcohols into aldehydes elongated by two carbon atoms.

Ruthenium-catalyzed direct α-alkylation of amides using alcohols

The highly efficient direct α-alkylation of unactivated amides has been accomplished using alcohols in the presence of the Ru-PNN catalyst (0.1 mol%) with a high turnover number. Using this approach, 2-oxindole was directly transformed into C3-alkylated 3-hydroxyindolin-2-one in one step without the use of any oxidant.