Palladium‐Catalyzed Carbonylative Multicomponent Reactions

Abstract

The achievements on palladium-catalyzed carbonylative multicomponent reactions (CMCR) have been summarized and discussed according to the type of carbonylation reaction involved.

Creation of Novel Toxic Gas Surrogates and the Development of Safe and Facile Catalytic Reactions

“…Monosubstituted alkenes were good substrates, and the 1,1-disubstituted alkene only afforded the linear product in moderate yield, indicating that steric factors determined both reactivity and regioselectivity (entries 3-5). While cyclic 1,2-disubstituted alkenes such as norbornene and indene reacted well, stilbene as an acyclic example required high temperature conditions due to its low reactivity (entries [6][7][8].…”

“…44) To confirm whether hydroesterification proceeds directly through the formate or via decarbonylation of the formate, the catalytic hydroesterification of 5 was conducted using the 13 C-labeled formate 6-13 C (Chart 4). While the desired products (7)(8)(9)(10)(11)(12)(13) C and 8-13 C) were obtained in high yield, at most 60% of the 13 C label was incorporated into the two products. This result supports the notion that the CO ligand in Ru 3 (CO) 12 can be used as the carbonyl source for hydroesterification, and that the reaction proceeds via decarbonylation of the formate followed by recarbonylation of the Ru intermediate.…”

“…1) For example, carbon monoxide (CO), located at the center of C1 chemistry, 2) is naturally abundant and used in transition metal-catalyzed carbonylations to introduce carbonyl groups into various organic molecules. [3][4][5][6][7] Sulfur dioxide (SO 2 ) is mostly obtained by the oxidation of elemental sulfur collected from desulfurization processes in petrochemical plants, 8,9) and is used for the synthesis of industrially important sulfuric acid and its derivatives. 10) There are many points to consider and special equipment to be prepared in order to conduct experiments involving gases; they must be carried out in appropriate environments that ensure the safety of users while complying with relevant regulations.…”

(Z)-4-(Carbomethoxymethylene)-2-(4-fluorophenyl)-4H-benzo[d][1,3]oxazine

“…Palladium-catalyzed oxidative alkoxycarbonylation of alkynes is a simple and powerful tool for the synthesis of complex heterocyclic compounds from easily available starting reagents [1][2][3][4][5]. Over the years, we have successfully applied this effective methodology to access carbonylated compounds in a one-pot fashion [6][7][8][9][10][11][12][13].…”

Mechanochemical Palladium‐Catalyzed Carbonylative Reactions Using Mo(CO)6

“…Specifically,t he use of metal carbonyls as one-carbon building blocksi np alladium-catalyzed carbonylation reactions, such as alkoxycarbonylations and aminocarbonylations, was envisaged (Scheme 1b). [15] Herein, we report the findings on our investigation,w hich include the development of as olvent-free protocol for the palladium-catalyzed carbonylation by ball milling, the in situ pressurem onitoring of the reaction, and the application of the mechanochemicala pproacht ot he synthesis of series of esters and amides.…”