Heterogeneous One-Pot Carbonylation and Mizoroki–Heck Reaction in a Parallel Manner Following the Cleavage of Cinnamaldehyde Derivatives

4 years ago

Heterogeneous One-Pot Carbonylation and Mizoroki–Heck Reaction in a Parallel Manner Following the Cleavage of Cinnamaldehyde Derivatives

Hironao Sajiki, Yoshinari Sawama, Tomohiro Hattori, Shun Ueda, Yasunari Monguchi, Ryoya Takakura

Carbon monoxide (CO) and styrene derivatives that can be both generated by a palladium on carbon (Pd/C)-catalyzed carbon–carbon (C−C) bond cleavage reaction of cinnamaldehyde derivatives were effectively utilized in further palladium-catalyzed C−C bond forming reactions in a direct and practical way. CO derived from simple and affordable CO carriers such as cinnamaldehyde or terephthalaldehyde was efficiently employed in the in situ CO fixation with various aromatic iodides through a palladium-catalyzed carbonylation followed by an inter- or intramolecular coupling reaction with alcohols to afford the corresponding esters or lactones, respectively. Styrene derivatives were also efficient substrates in an in situ Mizoroki–Heck-type cross-coupling reaction with aryl iodides, leading to the effective formation of asymmetric stilbenes. The decarbonylation of cinnamaldehyde derivatives and the subsequent independent syntheses of both esters/lactones and 1,2-diarylethenes could be achieved in a virtual one-pot and in situ reaction using a H-shaped pressure-tight glass-sealed tube consisting of two independent but laterally connected reaction tubes in the gas space. One-pot wonder! Carbon monoxide and styrene, generated by a palladium on carbon (Pd/C)-catalyzed carbon–carbon (C−C) bond cleavage reaction of cinnamaldehyde, were employed for simultaneous Mizoroki–Heck and carbonylation reactions. The procedure was used for the one-pot synthesis of esters, lactones, and 1,2-diarylethenes.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201606048