Ferrocene products

A complication that does not extend to other aromatics exists in ferrocene metalation. This is heteroannular dimetalation, which gives products that often contaminate the desired 2-metalation product. This phenomenon was investigated in one instance and from metalation of dimethylaminomethylferrocene with excess n-butyllithium, the l,2,l -tri-substituted product shown in Reaction 3 was isolated (10). Considerable amounts of a l,2,l -trisubstituted ferrocene product could also be isolated... 

In addition, analogous ferrocene products, 75, were synthesized, where the R in 73 is a 1,1 -ferrocene unit. Product yields were about 50% the reaction is completed within several seconds. 

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]. 

The cooled contents of the 2S0-ml. flask containing ferrous chloride (Note 6) are added to the cold sodium cyclopentadienide solution while passing a stream of nitrogen through both flasks. The combined mixture is stirred for 1.25 hours at a temperature just below reflux. Solvent is removed by distillation, and the ferrocene is extracted from the residue with several portions of refluxing petroleum ether (b.p. 40-60°). The product is obtained by evaporation of the petroleum ether solution. Ferrocene may be purified by recrystallization from pentane or cyclohexane (hexane, benzene, and methanol have also been used) or by sublimation. The 3ueld is 31-34 g. (67-73%) (Note 7), m.p. 173-174°. 

Friedel-Crafts acylation involves electrophilic attack by acyl cation (CHsCO ) on the ring, and the ring s electronic character should indicate its susceptibility to attack. Compare electrostatic potential maps of ferrocene and acetylferrocene. Which molecule contains the most electron-rich ring Which acylation reaction should be faster Does an acetyl substituent enhance or diminish ring reactivity What should be the major product when ferrocene is combined with one equivalent of acetic anhydride ... 

Hie necessity of an anionic tbiolale ligand was established by perforniing reactions with ferrocene tliioetliets 37 as ligands. Here, essentially racemic products... 

Column Chromatography Column Chromatography is a useful separation technique for mixtures resulting from intermediate to small scale synthetic processes. For example, nitroferrocene is conveniently isolated from a mixture of the product, ferrocene, and l,r-dinitroferrocene by chromatography on Activity I basic alumina at about the 100-g scale (Chapter 7, Section XI). 

Singer and co-workers have investigated the acylation reactions of ferrocene in ionic liquids made from mixtures of [EMIMJI and aluminium(III) chloride (Scheme 6.1-5) [9, 10]. The ionic liquid acts both as solvent and as source of the Friedel-Crafts catalyst. In mildly acidic (X(A1C13) > 0.5 [EMIM]I/A1C13, the monoacetylated ferrocene was obtained as the major product. In strongly acidic [EMIM]I/AlCl3 X(A1C13) = 0.67 the diacylated ferrocene was the major product. Also, when R = alkyl, the diacetylated product was usually the major product, but for R = Ph, the monoacetylated product was favored. 

The crude product from the above reaction mixt was fractionated into a distilled product (bp 200°/0.3 Torr) with an average molecular weight of 514 and a residue with an average molecular weight of 940. These were evaluated as catalysts and compared to prior art ferrocenes in a standard carboxy-terminated polybutadiene formula cured with MAPO. The results are shown in Table 31... 

The high enantioselectivity again can be rationalized by enantioface-selective alkene coordination in 63 (Fig. 35). The olefin moiety is expected to bind trans to the upper imidazoline moiety [70,73] thereby releasing the catalyst strain. Coordination at this position may, in principal, afford four different isomers assuming the stereoelectronically preferred perpendicular orientation of the alkene and the Pt(II) square plane. In the coordination mode shown, steric repulsion between both olefin substituents and the ferrocene moiety is minimized. Outer-sphere attack of the indole core results in the formation of the product s stereocenter. 

MEMED has also been used to investigate the nature of coupled ion-transfer processes involved in spontaneous electron transfer at ITIES [80]. In this application, a key strength of MEMED is that all of the reactants and products involved in the reaction can be measured, as shown in Figs. 19 and 20. The redox reaction studied involved the oxidation of either ferrocene (Fc) or decamethylferrocene (DMFc) in a DCE phase (denoted by Fcdce) by either IrCle or Fe(CN)g in the aqueous phase (denoted by Ox ) ... 

Transition metal complexes containing Si-OH groups have been isolated in low yield after hydrolysis of the products formed in the reaction between (Me2N)2SiCl2 and ferrocene under Friedel-Crafts conditions [Eq. (25)] (151). 

Togni and co-workers have used the convergent methodology to link phosphine-containing chiral ferrocene ligands on the cyclophosphazene core to obtain dendrimeric structures of the type 37 (Fig. 21) (201). The reaction with the cyclophosphazene end occurs by the replacement of the P-Cl bond and by the formation of the P-0 bond. The dendrimers contain twelve and sixteen ferrocene moieties respectively. The phosphine units present can coordinate to Rh(I) to afford metallic dendrimers, which have been shown to be excellent catalysts for the enantioselective hydrogenation of dimethyl itaconate. The product... 

Attempted acetylation of 2,2, 5,5 -tetramethyl-l,l -distibaferrocene (29) or 3,3, 4,4 -tetramethyl-l,T-distibaferrocene (61) led to destruction of the ring system and the formation of intractable products. Acid-catalyzed H/D isotopic exchange (Scheme 14) is the simplest electrophilic aromatic substitution. Both l,T-diphosphaferrocene55 (7) and l,l -diarsa-ferrocene (8)13 undergo rapid exchange at the a positions when treated... 

Photodimerization of isoprene has also been observed using ferrocene as sensitizerproduct distribution in this case was similar to that observed using high-energy photosensitizers. To account for this behavior, the following mechanism was proposed, where 7 indicates a triplet level of isoprene higher than the lowest triplet ( ) ... 

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