Masao Hisatome

Organometallic compounds : XXIII. Formation of novel di- and tri-bridged ferrocenophanes

Abstract Treatment of 2-(2-carboxyethyl)[4](1,1′)ferrocenophane with trifluoroacetic anhydride gave three isomeric products IV, V and VI; cyclized at the 3-, 3′- and 2′-positions, respectively. The same reaction of 4-(2-carboxyethyl)[4](1,1′)[4]-(3,3′)ferrocenophane also gave three multibridged products XXVII, XXVIII and XXIX, cyclized at the 5-, 5′- and 4′-positions, respectively. The di- and tri-bridged ferrocenes V and XXVIII linked between dissymmetric positions, “twist ferrocenophanes”, are novel ferrocenophanes. Some reactions of the multi-bridged ferrocenophanes are described.

Organometallic compounds : XII. stereochemical interconversion reactions between 1,1′−bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes

Abstract Meso and racemic isomers of 1,1′-bis(α-hydroxyalkyl)ferrocene derivatives, and trans and cis isomers of 7-oxa[3]ferrocenophanes have been isolated. The configurations of these isomers have been determined both by spectroscopy and from their reaction behavior. It has been found that the ring-closure and ring-opening interconversion reactions between 1,1′-bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes are stereospecific. PMR spectra of the diols and ethers have been examined at 100 MHz in CF 3 COOH, and the existence of α-[1′-(α-hydroxyalkyl)ferrocenyl]carbonium ions has been demonstrated in this acid. A mechanism for the various interconversion reactions is proposed on the basis of their stereospecific reactivity and from the PMR spectra of the carbonium ions.

Organometallic compounds : XXI. Syntheses of [4](1,1′)[4](3,3′)ferrocenophane and related compounds☆

Abstract Synthesis of [4](1,1′)[4](3,3′)- and [4](1,1′)[3](3,3′)ferrocenophanes were attempted via two routes. Bridge enlargement of [3][3]ferrocenophane-6,11-dione with CH 2 N 2 afforded [4][4]ferrocenophane-7,12-dione (IX), [4][3]ferrocenophane-6,11-dione, and [4][4]ferrocenophane-6,7,12-trione. [4][3]Ferrocenophane-6-one (XXII) was prepared from [4]ferrocenophane. Reaction of the ketone XXII with CH 2 N 2 gave [4][4]ferrocenophane-7-one (XXIII). The reduction product of the ketone XXIII was identical with that of the diketone IX. Bridge enlargement reactions of other ferrocenophanes are also described.

Design of a novel artificial nucleobase for the selective formation of a triple-complex with a cytosine-guanine base pair

Abstract A new artificial nucleobase (1) was designed for the selective formation of a triple-complex with a cytosine-guanine base pair at the major groove site. It has been proved based on the 1D- and 2D 1H-NMR spectra that the protected 2′-oxy-1 (7) forms a triplex complex with the GC pair selectively.

A package compound of a metal atom with a hydrocarbon [4][4][4][4][3](1,2,3,4,5)ferrocenophane

Abstract Perbridged ferrocenes ( 9 and 11 : the title compound) have been synthesized and characterized by spectroscopies and X-ray diffraction, and an interesting rotational disorder has been found by the X-ray crystal analyses of both 9 and 11 .

Bridged ferrocenes : VII. Synthesis of di- and tri-bridged ferrocenes with pentamethylne chains☆

Abstract Double or successive bridge-enlargement reactions were used on appropriate α-ketones followed by reduction to prepare 1,1′-pentamethyleneferrocene, VIII, 1,1′,3,3′-bis(pentamethylene)ferrocene, XX, and 1,1′,2,2t,4,4′-tris(penta-methylene)ferrocane, XXX. The bridge-enlarging reactions are discussed, and the PMR spectral behavior of the polybridged ferrocenes is briefly discussed.

Organometallic compounds XXVIII. Intermolecular carbon—carbon bond formation by oxidation of (1-arylvinyl)ferrocenes with molecular oxygen in the presence of silica gel

Abstract Treatment of (1-hydroxy-1-arylethyl)ferrocenes (VII) or (1-arylvinyl)ferrocenes (VIII) in hexane with O 2 gas in the presence of silica gel gave oxidative dimerization products; butadiene (XI), tetrahydrofuran (XII) and butan-1,4-diol (XIII) derivatives. It is suggested that the dimers were produced via six-membered cyclic peroxide formed by incorporation of a molecular oxygen into two olefin molecules.

Synthesis of ferrocenoporphyrinophanes stacked with metals and aromatic rings

Abstract Double and triple layered porphyrinophanes bridged with 1,1′- or 1,3-disubstituted ferrocene moieties and their iron complexes have been synthesized.

Synthesis of [4][34](1,2,3,4,5)ferrocenophane

Abstract The title compound ( 3 ), the first example of bridged ferrocene with four trimethylene chains, has been synthesized. The d-d* absorption band of 3 appears at unusually short wavelength (345 nm, ferrocene: 443 nm).

Organometallic compounds. XXXIX: Synthesis and X-ray crystal structure of [4][3][4][3](1,2,3,4)ferrocenophane

Abstract [4][3][4][3](l,2,3,4)FeiTocenophane (I) and some related tetrabridgedferrocenophanes have been synthesized via cyclization of 2-[4][4][3](l,3,4)ferroce acid with polyphosphate ester (PPE). Treatment of 5- [4][4][3](l,3,4)ferrocenophanepropanoic acid with PPE or polyphosphoric acid does not give an additionally bridged compound but a bridge-rearrangement product containing two homoannular rings. The crystal structure of I has been determined by X-ray diffraction. Compound I crystallizes in the monoclinic system, space groupP21/a with unit cell parametersa 17.490(4),b 8.489(1),c 12.157(2) «, β 101.51(1)°, andZ = 4. The two cyclopentadienyl (Cp) rings are in an eclipsed conformation and almost parallel to each other (dihedral angle, 1.1°). The bond lengths and angles in the Cp rings and methylene chains are normal but the distances between the Cp ring and the iron atom are unusually short (1.589 and 1.591 «) in comparison with multibridged ferrocenophanes containing tetramethylene chains.