27 Years of Catalytic Carbonylative Coupling Reactions in Hungary (1994–2021)

Abstract

Palladium-catalyzed carbonylation reactions, in the presence of nucleophiles, serve as very potent tools for the conversion of aryl and alkenyl halides or halide equivalents to carboxylic acid derivatives or to other carbonyl compounds. There are a vast number of applications for the synthesis of simple building blocks as well as for the functionalization of biologically important skeletons. This review covers the history of carbonylative coupling reactions in Hungary between the years 1994 and 2021.

Alkyl Levulinates and 2-Methyltetrahydrofuran: Possible Biomass-Based Solvents in Palladium-Catalyzed Aminocarbonylation

“…Carboxamides can be synthesized from easily available starting materials with aminocarbonylation, although the conventional carboxylic acid−carboxylic halide−carboxamide route is difficult to prepare because it has no notable yield in the implementation [ 29 , 30 ]. Moreover, our research group has been investigating this reaction in the conventional solvent DMF for years [ 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ], and thanks to the ascertainments of the groups from Skrydstrup [ 40 ] and Mika [ 41 , 42 , 43 ], our interest has been turned to the investigation of green solvents.…”

Highly Chemoselective One‐Step Synthesis of Novel N‐Substituted‐Pyrrolo[3,4‐b]quinoline‐1,3‐diones via Palladium‐Catalyzed Aminocarbonylation/Carbonylative Cyclisation Sequence

“…[26] Surprisingly, as far as we could ascertain, no palladiumcatalyzed aminocarbonylation reaction of quinoline-2,3-dihalide has been previously documented. Therefore, following our interest in such effective homogenous catalytic transformations during the last decades, [27] it seemed to be conceivable to provide novel N-substituted-pyrrolo [3,4-b]quinoline-1,3-diones, via palladium-catalyzed carbonylative coupling process of 3bromo-2-iodoquinoline in the presence of various primary amines as N-nucleophiles. Furthermore, we presume that a subsequent intramolecular amidocarbonylation could occur in situ as a last stage of incorporation of the second CO leading to various pyrroloquinolinedione derivatives.…”

Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles

“…While several functional groups, i.e., C=C, C≡C, C–OH, etc., can be subjected to carbonylation, 3 the transformation of aryl–X compounds (X = I, Cl, or Br) and cheap and readily available CO in the presence of a nucleophile(s) represents a fundamental catalytic procedure for manufacturing various amides, carboxamides, carboxylic acids, esters, heterocycles, azides, etc. 4 However, it should be noted that several successful attempts were made to utilize an alternative CO source such as formaldehyde/paraformaldehyde, 5 formic acid, 6 etc., 7 due to the high toxicity of CO.…”

“…Since the discovery of hydroformylation and the Reppe reaction, the transition metal-catalyzed carbonylation reactions, providing facile and even atom-economic methods for the incorporation of the CO functionality into various skeletons, have become tremendously important in numerous fields of synthetic organic chemistry from laboratories to industrial applications. While several functional groups, i.e., CC, CC, C–OH, etc., can be subjected to carbonylation, the transformation of aryl–X compounds (X = I, Cl, or Br) and cheap and readily available CO in the presence of a nucleophile(s) represents a fundamental catalytic procedure for manufacturing various amides, carboxamides, carboxylic acids, esters, heterocycles, azides, etc . However, it should be noted that several successful attempts were made to utilize an alternative CO source such as formaldehyde/paraformaldehyde, formic acid, etc., due to the high toxicity of CO.…”