Tetracarbonylferrate reaction with alkyl halides

Applications of carbonylaie reactions in organic synthesis are numerous. Particularly noteworthy are schemes involving tetracarbonylferrate( - ID (referred to as Collman s reagent), which can be isolated as a. sodium salt, NanFe(CO)4-1.5 dioxane, and is commercially available. The highly nucleophilic [Fe(CO)4p reacts readily with alkyl halides to yield alkyl iron carbonylates ... 

Alkylation of disodium tetracarbonylferrate with alkyl halides and tosylates in the presence of ethylene provides ethyl ketones in a one pot procedure. Usage of alkenes for the second alkylation of Collman s reagent may provoke rearrangement reactions of the intermediate alkyliron species. This has been observed in a hexacyclic system where a ketone with a rearranged carbon skeleton was obtained in the course of this transformation. An analog of Collman s reagent is the [Fe(CO)3(NO)] anion, which can be applied in similar reactions. However, to date it has received less attention. ... 

The initial reaction between the alkyl halide (or p-toluenesulfonate) and disodium tetracarbonylferrate behaves as a typical Sn2-type substitution. Thus this step proceeds smoothly with primary and secondary reactants, but the tertiary analogs fail... 

Inversion of configuration (cf Epimerization) of alcohols (Mitsunobu reaction), 160-161, 286 of ally lie acetates with Pd, 27, 164 of allylpalladium with d-synthons, 27, 264 of alkyl halides or sulfonates by 1,3-dithiane anions, 22 by organylcuprates, 36 by tetracarbonylferrate<2 -X 46-47 in triorganylborane rearr., 37-38 of glycosides with free 2-OH by DAST, 272 of glycosyl halides, 271 of oxiranes by 1-alkync anions, 64, 204 by enolate type anions, 63-64 by internal alcoholate addition, 265 Inversion-esterification of alcohols, 160-161, 286 Inverted DNA , 345-346 Iodide, hydrogen porphyrin synthesis with, 255 Iodine = diiodine (Ij) ... 

Among other reactions, the bis-metallated species (151) derived from nitroalkanes condense with dialkyl carbonates to give comp>ounds (152), in 60—80% yield, which can serve as precursors of both a-amino-acids and a-hydroxyamino-esters as well as a-keto-esters. Oxazolin-5-ones (153) can be alkylated at the 4-position by alkyl halides in hot DMF containing HMPA and ethyldi-isopropylamine. Yields are good (60—90%) for allylic, benzylic, and propargylic halides but otherwise poor (e.g. 32% with EtI) under these conditions acid hydrolysis of the products affords substituted a-amino-acids. Mesoionic l,3-oxazol-5-ones (154), obtained from imidoyl chlorides and acyl-tetracarbonylferrates, react with alcohols to give N-acyl-a-amino-acid esters. ... 

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