Double carbonylation and beyond: systems at work and their organometallic models

Abstract

A quarter of a century after its (serendipitous) discovery, the catalytic sequential chaining of two carbon monoxides into an organic substrate (the so called double carbonylation reaction), is still not well understood. After a review of the most important experimental results, this Perspective proposes a critical survey of the main organometallic models and outlines some rather neglected tracks. Finally, the issue of the chaining of more than two carbon monoxides is also addressed.

Ring Closure of Alkoxycarbonyl(tetracarbonyl)pyruvoyliron Complexes into Metallalactones Induced by Nucleophilic Attack of Carbanions

“…The presence of these four IR bands and their frequencies suggested the formation of neutral cis disubstituted complexes. Under the same reaction conditions an analogous process was observed for 3(5) and 3(7), although the formed complexes rapidly evolved into Fe(CO) 5 and organic compounds . Complexes 2(1), 2(2), 2(3), 2(4), 2(6), 2(8), and 2(9), formed by reaction of 3(1), 3(2), 3(3), 3(4), 3(6), 3(8), and 3(9) with HCl, respectively, were obtained as pale-yellow crystals from a hexanes/ CH 2 Cl 2 (95:5) mixture at -30°C.…”

“…[7] To the best of our knowledge, prior to our study, only one example of nucleophilic addition at a carbonyl carbon of a ligand displaying a double C(O) chain had been described in the literature. In this paper, hydride was reported to attack the β carbonyl of a ligand of [(CO) 5 Mn{C(O)C(O)C 6 H 5 )}] to afford an anionic metallalactone by cyclization of the phenylglyoxyl with a terminal carbonyl. [12] These results prompted us to perform the cyclization of 1 with anionic nucleophiles (RO -, RS -, or R 2 P -).…”

“…It has also been shown that acyl ligands are less electrophilic than terminal carbonyl ligands. [5] In the course of a study of complexes considered as possible models for double or polycarbonylation reactions, we investigated the reactivity of compounds displaying a ligand with a C(O)C(O)R chain toward nucleophilic reagents. Indeed, addition of nucleophiles at C α of this type of ligand has been proposed to account for the formation of phenylpyruvic esters by dicarbonylation of organic halides catalyzed by [Co(CO) 4 ] -.…”

Production of phenylpyruvic acid from l-phenylalanine using an l-amino acid deaminase from Proteus mirabilis: comparison of enzymatic and whole-cell biotransformation approaches

“…In one method, PPA is synthesized from glycine and benzaldehyde at a 50 % transformation rate, producing many toxic byproducts (Villablanca and Cilento 1987). In another method, PPA is synthesized at high pressure from benzyl chloride and carbonic oxide using cobalt octacarbonyl as the catalyst-a process that is time-consuming and environmentally unfriendly (des Abbayes and Salaun 2003). Overall, since these methods cause environmental pollution, produce various byproducts, and have relatively low yields, the development of a method for PPA production that circumvents these disadvantages is highly desirable.…”

Thermal properties and reactions towards nucleophiles of an iron complex displaying an acetyl and a pyruvoyl ligands

“…However, their complexation to metals atoms efficient in catalytic carbonylation processes, gives rise to unstable species making the properties of these compounds difficult to evaluate. To appraise the possible intervention of complexes substituted by one or two of these organic carbonylated ligands in mono or poly carbonylation processes, the study of similar more stable complexes of Pt, Mn, Co, Fe have been performed [2,3]. In the course of our study of tricarbonylation reactions induced by iron models of the type cis(CO) 4 …”