620168-63-0Relevant academic research and scientific papers
Ferrocene compounds. XXXIX. 1-Ferrocenylisochromane
Cetina, Mario,Dakovic, Senka,Rapic, Vladimir,Golobic, Amalija
, p. m328-m330 (2003)
In the title compound, [Fe(C5H5)(C14H 13O)], the plane of the heterocyclic ring is almost perpendicular to the plane of the substituted cyclopentadienyl ring, and the heterocyclic ring adopts a half-chair conformation. The conformation of the nearly parallel cyclopentadienyl (Cp) rings [the dihedral angle between their planes is 2.7 (1)°] is almost halfway between eclipsed and staggered, and the rings are mutually twisted by about 19.4 (2)° (mean value). The mean lengths of the C - C bonds in the substituted and unsubstituted cyclopentadienyl ring are 1.420 (2) and 1.406 (3) A, respectively, and the Fe - C distances range from 2.029 (2) to 2.051 (2) A. The phenyl and unsubstituted cyclopentadienyl rings are involved in C - H...π interactions, with intermolecular H...centroid distances of 2.85 and 3.14 A for C - H...π(Ph), and 2.88 A° for C - H...π(Cp). In two of these interactions, the C - H bond points towards one of the ring bonds rather than towards the ring centroid. In the crystal structure, the C - H...π interactions connect the molecules into a three-dimensional framework.
Experimental and DFT study of cyclodehydration and acetylation of ferrocenyl diols
Lapi?, Jasmina,Vi?njevac, Aleksandar,Cetina, Mario,Djakovi?, Senka,Vr?ek, Valerije,Rapi?, Vladimir
, p. 7 - 15 (2012/07/16)
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 Et 2O. 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.
