Eckhard Paetzold

Palladium-Catalyzed Aminocarbonylation of Aliphatic Alkenes with N,N-Dimethylformamide as an In Situ Source of CO

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 inu2005situ 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.