Experimental and DFT study of cyclodehydration and acetylation of ferrocenyl diols

• Published in: Journal of molecular structure Vol. 1019; pp. 7 - 15
• Main Authors: Lapić, Jasmina, Višnjevac, Aleksandar, Cetina, Mario, Djaković, Senka, Vrček, Valerije, Rapić, Vladimir
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 18-07-2012
• Subjects: acetates; Acetylation; Biocatalysis; BP86 functional; cyclic ethers; Cyclodehydration; ethanol; Ferrocenyl diols; methanol; Penicillium camembertii; Reaction mechanism; triacylglycerol lipase; X-ray diffraction; Reaction mechanism; Cyclodehydration; Biocatalysis; Acetylation; BP86 functional; Ferrocenyl diols
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2012.03.071

► Synthesis and structural characterization of racemic ferrocenyl diols are presented. ► Ferrocenyl diols undergo intramolecular cyclodehydration reactions. ► Two different mechanisms of cyclization have been calculated at the BP86 level. ► Acetylations of ferrocenyl diols result in monoacetate products only.
Racemic ferrocenyl diols, i.e. ferrocenyl(2-hydroxymethylphenyl)methanol (2), ferrocenyl-2-(2-hydroxymethylphenyl)ethanol (7), and ferrocenyl(2-(2-hydroxyethyl)phenyl)methanol (9) have been prepared by reduction of corresponding ketoesters using NaBH4 in a mixture EtOH and Et2O. In the course of these reactions new cyclic ethers 1-ferrocenyl-2-oxaindane (3), 3-ferrocenylisochromane (8), and 1-ferrocenylisochromane (10) have been isolated as side-products. Intramolecular cyclizations of ferrocenyl diols occur in both acidic and neutral medium. Density functional theory (BP86) calculations were used to explain the mechanism of these cyclodehydrations. Acid catalyzed reaction follows the classical SN1 mechanism, whereas the cyclodehydration in neutral medium is described as an SN2 reaction. X-ray diffraction analysis of new cyclic ether products has been performed. Monoacetates 11, 13 and 15 have been obtained in the reaction of ferrocenyl diols 2, 7, and 9, respectively, and acetic anhydride. Stereoselective acylation of racemic diols by vinyl acetate have been catalyzed by various lipases, and the best stereoselectivity has been observed for the diol 2 in the presence of Penicillium camembertii lipase.