40286-74-6

Upstream product

• 56579-98-7 Lithium; 1-dimethylamino-ethenolate 
• 213380-00-8 C₂₂H₃₂N₂O₂SSi 
• 127-19-5 N,N-dimethyl acetamide 
• 122-97-4 3-Phenyl-1-propanol 
• 2270-20-4 5-Phenylpentanoic acid 
• 124-40-3 dimethyl amine 
• 20371-41-9 5-phenylvaleric acid chloride 

Downstream Products

• 36884-28-3 5-phenyl-1-pentanal 
• 62101-01-3 N,N-dimethyl-5-phenylpentan-1-amine 
• 10521-91-2 5-phenylpentan-1-ol 
• 110145-91-0 N,N-dimethyl-1,5-diphenylpentan-1-amine 
• 839721-04-9 (4R)-4-Methyl-4-{2-[1-methyl-4-(5-phenylpentanoyl)pyrrol-2-yl]ethyl}-1,3-oxazolidin-2-one 

Relevant academic research and scientific papers

Sustainable Alkylation of Unactivated Esters and Amides with Alcohols Enabled by Manganese Catalysis

The first example of manganese-catalyzed C-alkylation of the carboxylic acid derivatives is reported. The bench-stable homogeneous manganese complex enables the transformation of the renewable alcohol and carboxylic acid derivative feedstock to higher value esters and amides. The reaction operates via hydrogen autotransfer and ideally produces water as the only side product. Importantly, aliphatic-, benzylic-, and heterocyclic-containing alcohols can be used as alkylating reagents, eliminating the need for mutagenic alkyl halides.

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.

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 %).

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.

The extraordinary reactions of phenyldimethylsilyllithium with N,N-disubstituted amides

The reactions of the silyllithium reagent with tertiary amides was discussed. The enediamines were easily isomerized from cis to trans, easily oxidized to dienediamines and were hydrolyzed to α-aminoketones. If the two equivalents of the silyllithium reagent were used, the product was an α-silylamine. The results show that each member of the homologous series of amides gives rise to a substantially different product.