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Ring Closure of Alkoxycarbonyl(tetracarbonyl)pyruvoyliron Complexes into Metallalactones Induced by Nucleophilic Attack of Carbanions
Author(s) -
Cabon Patrice,
Rumin René,
Salaün JeanYves,
des Abbayes Hervé,
Triki Smail
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500997
Subject(s) - chemistry , carbanion , nucleophile , diethyl malonate , moiety , ring (chemistry) , medicinal chemistry , ligand (biochemistry) , dimethyl malonate , malonate , stereochemistry , nucleophilic addition , enantioselective synthesis , catalysis , organic chemistry , biochemistry , receptor
The reaction of carbanions with the pyruvoyl‐substituted iron complex [(CO) 4 Fe(CO 2 CH 3 ){C(O)C(O)CH 3 }] ( 1 ) affords the anionic trifunctionalized metallalactones [(CO) 3 Fe{C(O)C(CH 3 )(CRR′R″)OC 4 (O)(Fe–C 4 )}(CO 2 CH 3 )] – ( 3 ), whose formation results from the addition of the nucleophile to the β carbonyl of the pyruvoyl moiety, followed by attack of the oxygen of this β carbonyl on a terminal carbonyl ligand. These anionic lactones react, at low temperature, with HCl to give rise to the neutral lactones [(CO) 4 Fe{C(O)C(CH 3 )(CRR′R″)OC 4 (O)(Fe–C 4 )}] ( 2 ), which were previously obtained by addition of NuH nucleophiles to 1 . Complex 3(3) , whose lactonic ring formation has been performed using the diethyl malonate anion (R = R′ = CO 2 C 2 H 5 ; R″ = H), and the dimethyl‐substituted neutral lactone 2(1) (R = R′ = R″ = H) have been characterized by X‐ray diffraction studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)