Ferrocenyl carbaldehyde

The most useful ferrocene derivatives for the development of functional ferrocene chemistry are acetylferrocene, ferrocenyl carbaldehyde, ferrocenyl lithium and... 

Pyridyl alkanol [41], diol [42], and ferrocenyl alcohol [43] were the first asymmetric autocatalysts found by Soai and co-workers in the enantioselective alkylation of pyridine-3-carbaldehyde, dialdehyde, and ferrocenecarbaldehyde, respectively, with dialkylzincs. 

Chiral diol 52 [52] and ferrocenyl alkanol 54 [53] also work as asymmetric autocatalysts in the enantioselective addition of dialkylzincs to the corresponding dialdehyde 51 and ferrocene-carbaldehyde 53, respectively (Scheme 9.26). 

Several interesting derivatives of tpy have been prepared in which a ferrocene is linked to the 4 -position. The condensation of ferrocene carbaldehyde with 2-acetyl pyridine leads to the parent system (31a).34 Alternatively, l,5-bis(2-pyridyl)-3-(ferrocenyl)pentane-l,5-dione may be easily prepared in 77% yield, and subsequent treatment with ammonium acetate provides a 78% yield of (31a).35 If ferrocene l,l -dicarbaldehyde is used in the first procedure, the bisterpyridyl ferrocene can be synthesized.36 Addition of the anion derived from (25i) to ferrocene carbaldehyde affords the alcohol (31b), which can be dehydrated to the ethylene derivative (31c).37 Coupling of alkynyl ferrocene with the bromo-derivative (25e) leads to a tpy linked to ferrocene by a phenylacetylene bridge (31d).38... 

Hosseini-Sarvari (2011a) reported solvent-free selective synthesis of ferrocenyl ami-nophosphonic esters (159) by treating ferrocene carbaldehyde (157) with different aromatic and aliphatic amines (47) and dialkyl phosphate (158) in the presence of nano-ZnO (Scheme 9.51). For these reactions, several other catalysts such as CuO, MgO, basic AI2O3, nano-TiOj, Mg(C104)2, and so on were screened, but the results showed excellent activity for the nano-ZnO catalyst. No formation of imines or a-OH phospho-nates was observed. After completion of the reaction, the reaction mass was diluted with ethyl acetate and centtifuged to separate the catalyst. The separated organic layer was concentrated and the products were purified by chromatography on cellulose. 

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