101. Cyclization of the pyruvyl(methoxycarbonyl)tetracarbonyliron complex cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) induced by pronucleophile reagents
- Author
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Marek M. Kubicki, Hervé des Abbayes, Jean-Yves Salaün, Murielle Sellin, Véronique Patinec, Patrice Cabon, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Inorganic Chemistry ,010405 organic chemistry ,Stereochemistry ,Chemistry ,Reagent ,Organic Chemistry ,Atom (order theory) ,[CHIM]Chemical Sciences ,Physical and Theoretical Chemistry ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences - Abstract
International audience; Two iron complexes, cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) (1a) and cis-(CO)4Fe[C(O)CO2-CH2] [C(O)CH2] (3), are reported. Each complex can be considered as a λ-keto ester with a metal atom inserted into the chain linking its two organic groups. 1a is the only one found to evolve thermally, similarly to organic λ-keto esters, into the methoxy metallalactone (CO)4FeC(O)C(CH3)(OCH3)OC(O) (2a). This reaction is not reversible and does not require any acid or alkaline catalysis. The process does not result from a spontaneous dissociation of the methoxycarbonyl ligand of la but from an associative intra or intermolecular mechanism. A similar process can also be induced by pronucleophile reagents, and it affords a series of substituted metallalactones: (CO)4FeC(O)C(CH3)(Nu)OC(O) (Nu = OCH3 (2a), OC2H5 (2b), SC2H5 (2c), P(C6H5)2 (2d), P(C6H11)2 (2e)). Complex 2e has been characterized structurally. These substituted lactones are formed by nucleophilic attack of the reagent at the pyruvyl β-carbonyl followed by carbonylate attack on the alkoxycarbonyl ligand.
- Published
- 2002
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