5830-30-8Relevant articles and documents
Palladium-Catalyzed Aminocarbonylation of Aliphatic Alkenes with N,N-Dimethylformamide as an in Situ Source of CO
Seidensticker, Thomas,Furst, Marc R. L.,Frauenlob, Robin,Vondran, Johanna,Paetzold, Eckhard,Kragl, Udo,Vorholt, Andreas J.
, p. 4085 - 4090 (2015)
The palladium-catalyzed aminocarbonylation of aliphatic alkenes is presented for the first time without the need for external CO pressure. N,N-dimethylformamide (DMF) is used as an in situ source of both the required carbon monoxide and the amine substrate. The applied palladium catalytic system is well-known for a number of carbonylation reactions, including those with CO surrogates and tandem isomerizing carbonylations. The reaction pathway was investigated and proved to proceed by an acid-catalyzed DMF decomposition to CO and dimethyl amine with subsequent aminocarbonylation of the alkene. Pressure-versus-time curves gave more insight into the correlation between acid concentration and aminocarbonylation activity. Aliphatic alkenes (terminal and internal) are transformed, also in commercial glassware, into the corresponding linear N,N-dimethylamides with excellent selectivities. Hence, amide synthesis by aminocarbonylation moves closer to application in standard organic laboratories. Do-it-yourself CO production: The aminocarbonylation of alkenes for aliphatic amide synthesis is presented for the first time using N,N-dimethylamine as an in situ source of both, the required CO and dimethylamine. Excellent selectivities to the linear product are ensured by isomerizing carbonylation applying a [Pd]/1,2-DTBPMB system. 1,2-DTBPMB=1,2-bis((di-tert-butylphos- phino)methyl)benzene.
Amine-boranes as Dual-Purpose Reagents for Direct Amidation of Carboxylic Acids
Choudhary, Shivani,Hamann, Henry J.,Ramachandran, P. Veeraraghavan
supporting information, (2020/11/13)
Amine-boranes serve as dual-purpose reagents for direct amidation, activating aliphatic and aromatic carboxylic acids and, subsequently, delivering amines to provide the corresponding amides in up to 99% yields. Delivery of gaseous or low-boiling amines as their borane complexes provides a major advantage over existing methodologies. Utilizing amine-boranes containing borane incompatible functionalities allows for the preparation of functionalized amides. An intermolecular mechanism proceeding through a triacyloxyborane-amine complex is proposed.
A highly efficient catalytic α-alkylation of unactivated amides using primary alcohols
Yao, Wubing,Ma, Xiaochen,Guo, Le,Jia, Xiangqing,Hu, Aiguo,Huang, Zheng
supporting information, p. 2919 - 2921 (2016/06/13)
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 %).
