Ferrocene derivative

The asymmetric cyclopalladation of dimethylaminomethylferrocene takes place in the presence of an optically active carboxylic acid (e.g, A -acetylvaline), giving the cyclopalladation product 478 in 78% ee, from which optically active ferrocene derivatives were prepared[434]. 

Other interesting synthetic applications of the ketone-derived enamine alkylation are found in the monomethylation of steroid enamines (249), extension of the benzylation reaction (250) to a ferrocene derivative (251), the use of a-bromoesters (252) and ketones (252) or their vinylogues (25J), in the syntheses of alantolactone (254-256), isoalantolactone (257), and with a bridged bis-enamine (258). The use of bifunctional alkylating agents is also seen in the introduction of an acetylenic substituent in the synthesis of the characteristic fragrant constituent of jasmine (259), the synthesis of macrocyclic ketolactones (260), the use of butyrolactone (261), and the intermolecular or intramolecular double alkylations of enamines with dihalides (262). 

Interestingly, the ferrocene derivative 12 reacted with NH2OH HCl in pyridine to give furazan 13 in 46% yield (86ZOB1110) (Scheme 4). 

Harrowfield et al. [37-39] have described the structures of several dimethyl sulfoxide adducts of homo bimetallic complexes of rare earth metal cations with p-/e rt-butyl calix[8]arene and i /i-ferrocene derivatives of bridged calix[4]arenes. Ludwing et al. [40] described the solvent extraction behavior of three calixarene-type cyclophanes toward trivalent lanthanides La (Ln = La, Nd, Eu, Er, and Yb). By using p-tert-huty ca-lix[6Jarene hexacarboxylic acid, the lanthanides were extracted from the aqueous phase at pH 2-3.5. The ex-tractability is Nb, Eu > La > Er > Yb. 

A variable-temperature NMR spectroscopic study of the titanium(IV) complex 43 also indicated free rotation of the five-membered rings, but, as in the ferrocene derivative 38 allowed the determination of the activation barrier for the phenyl ring rotation (AG (-90 °C) = 9.8 0.5 kcal mol1). 

The burning rates of standard aluminized hydrocarbon binder composite proplnts may be increased significantly not only with ferrocene derivatives but also with compatible carborane-type burning rate additives. However, most ferrocene derivatives are volatile solids or liquids which have a tendency to evaporate from the proplnt during storage, thereby degrading ballistic performance. Rudy (Ref 71) minimized this problem by the use of polynuclear ferrocene... 

RELATIVE REACTIVITIES OF REACTION OF FERROCENE DERIVATIVES WITH MeCOCl... 

Palladacycles are defined as compounds with a Pd-C CT-bond with the Pd being stabilized by one or two neutral donor atoms, typically forming 5- or 6-membered rings [51]. Ferrocenyl palladacycles constitute a particularly attractive catalyst class partly due to the element of planar chirality. The first diastereoselective cyclopallada-tion of a chiral ferrocene derivative was reported in 1979 by Sokolov [52, 53]. 

Bolts JM, Wrighton MS (1978) Chemically derivatized n-type semiconducting germanium photoelectrodes. Persistent attachment and photoelectrochemical activity of ferrocene derivatives. J Am Chem Soc 100 5257-5262... 

Fukuzumi S, Okamoto K, Gros CP, Guilard R. 2004. Mechanism of four-electron reduction of dioxygen to water by ferrocene derivatives in the presence of perchloric acid in benzonitrile, catalyzed by cofacial dicobalt porphyrins. J Am Chem Soc 126 10441. 

The first monosubstituted ferrocene derivatives containing chiral amino-sulfide backbones in the side chain were reported by Bonini et These... 

Scheme 10.13 1,3-Dipolar cycloadditions of azomethine ylides with ferrocene-derived S/P ligands and AgOAc.

III. SELECTIVE ION TRANSFER AT THE W/0 INTERFACE COUPLED WITH REDOX REACTIONS BETWEEN FLAVIN MONONUCLEOTIDE IN W AND A FERROCENE DERIVATIVE IN O AND CO2 EVOLUTION [19,21]... 

The intramolecular insertion of a sulphonyl nitrene into a side-chain methyl group to give 36 and 37 has already been mentioned, as has the intramolecular cyclization of ferrocenylsulphonyl azide to give the bridged ferrocene derivative (17). 

In addition to the ferrocene-derived polymers, there have been reports of a few other metal-containing polymers with incorporated boron atoms. One such polymer... 

Jaworska-Augustyniak, A., Transition Met. Chem., 1979, 4, 207-208 Contact of tetranitromethane with ferrocene under various conditions leads to violent explosions, though not if the latter is dissolved in methanol or cyclohexane. Other ferrocene derivatives react violently, but not the dimethyl compound. 

Other remarkable examples showcasing the synthetic potential of this approach concern the preparation of decamagnesiated and decazincated ferrocene derivatives from the corresponding decakis(chloromercurio)ferrocene complex 142 (Scheme 19).177 178... 

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