Mikami studies

Taniguchi K. and Mikami S. (1985). Fine structure of the epithelia of vomeronasal organ in horses and cattle a comparative study. Cell Tiss Res 240, 41-48. 

Katagi T, Mikami N, Matsuda T, Miyamoto J (1989) Molecular orbital and experimental studies on the photoinduced decarboxylation of pyrethroid model esters. J Chem Soc Perkin Trans 2 779-782... 

A. Fujii, S. Enomoto, M. Miyazaki, and N. Mikami, Morphology of protonated methanol clusters An infrared spectroscopic study of hydrogen bond networks of H+(CH30H)n (n 4 15). 

V. Venkatesan, A. Fujii, T. Ebata, and N. Mikami, Infrared and ab initio studies on 1,2,4,5 tetrafluorobenzene clusters with methanol and 2,2,2 trifluoroethanol Presence and absence of an aromatic C H O hydrogen bond. J. Phys. Chem. A 109, 915 921 (2005). 

Hachiya, K., M. Sasaki, Y. Saruta, N. Mikami, and T. Yasanuga (1984), "Static and Kinetic Studies of Adsorption-Desorption of Metal Ions on the Y-AI2O3 Surface", J. Phys. Chem. 88, 23-31. 

Figure 3 shows the pH dependence for phosphate adsorption on YAI2O3 for a phosphate concentration of 8 x 10 3 mol dm-3, at 1= 1.5xlO-2M, [P] = 30 g dm-3, and 25°C. It is well known that below the pHZpC in the absence of phosphate, both the surface- and C-potential in the -y—AI2O3 suspension are positive however in the presence of phosphate, the surface is negatively charged at pH values below the zpc (pH = 8.5 indicating specific adsorption of phosphate (see Figure 4). A mechanism to explain phosphate adsorption based on pressure-jump studies has been postulated by Mikami et al. (15)...

Hachiya, K., Sasaki, M., Saruta, M., Mikami, N. Yasunaga, T. 1984. Static and kinetic studies of adsorption-desorption of metal ions on a... 

Kishi, Mikami and Nakai125 have studied the intramolecular acylation of trimethylsilyl alkenoyl chlorides, using aluminium trichloride. They found two possible outcomes. 5-Trimethylsilylhept-5-enoyl chloride 100 cyclized in the expected fashion (a-cyclization)... 

N. Mikami, Spectroscopic study of intracluster proton transfer in small size hydrogen-bonding clusters of phenol, Bull. Chem. Soc. Jpn, 68 (1995) 683-695. 

Mikami et al. studied the Diels-Alder reaction between a-methylstyrene and n-butyl glyoxylate catalyzed by a titanium binolate catalyst.76-78 Addition of 0.5 equivalents of (Zf)-BINOL to 1 equivalent of the racemic catalyst accelerated the reaction and gave the product with 89.8% ee (Scheme 20). Enantiopure catalyst derived solely from (/ )-BINOL gave the product with 94.5% ee. Here the amplification originates from the creation of a new chiral complex 9 of higher efficiency (rate and enantioselectivity) with respect to each enantiomer of the original racemic catalyst. 

Most studies of proton transfer in aromatic molecules concern phenol (Abe et al. 1982a,b,c Fuke and Kaya 1983 Gonohe et al. 1985 Jouvet et al. 1990 Lipert and Colson 1988 Mikami et al. 1987, 1988 Oikawa et al. 1983 Solgadi et al 1988 Steadman and Syage 1990 Syage 1990 Syage and Steadman 1991) or 1-naphthol (Cheshnovsky and Leutwyler 1985, 1988 Knochenmuss et al. 1988 Knochenmuss and Leutwyler 1989). These compounds can be associated with various proton acceptors ammonia, water, methanol, monoethylamine, piperidine, etc., differing essentially by their different gas phase proton affinities. 

Ammonia is well known to be a strong nucleophile. The nucleophilic substitution reactions in the ionized clusters of X-benzene (X = F, Cl) have been widely studied (Brutschy 1989, 1990 Brutschy et al. 1988, 1991 Mayeama and Mikami 1988, 1990, 1991 Riehn et al. 1992). All these experiments clearly show a specific behaviour not encountered in the hydroxylic solvents depending on the substituted aromatic and the cluster size, two types of substitution reaction can be detected. The first type leads to ionic amines by substitution of X by the -NH2... 

The authors are deeply indebted to the work of all collaborators and co-workers whose names are listed in the references of this chapter (in particular, S.F. Prof K. M. Kadish, Prof K. Mikami and Prof O. Ito DMG Prof K.-D. Asmus, Prof M. Maggini, Prof N. Martin and Prof M. Prato). S.F. acknowledges continuous support of his study on electron-transfer chemistry by a Grant-in-Aid from the Ministry of Education, Science, Culture and Sports, Japan. D.M.G. acknowledges the support by the Office of Basic Energy Sciences of the Department of Energy. This is document NDRL-4267 from the Notre Dame Radiation Laboratory). We would like to thank Drs. H. Imahori and C. Luo for their helpful discussion. 

As part of a series of studies on the use of BINOL-Ti(IV) complex 53 as a catalyst in a number of C-C bond-forming reactions, Mikami has reported the aldol addition reactions of thioacetate-derived silyl ketene acetals 55, 56 to a collection of highly functionalized aldehydes (Eq. (8.13)) [28]. As little as 5 mol% of the catalyst mediates the addition reaction and furnishes adducts 57 in excellent yields and up to 96% ee. One of the noteworthy features of the Mikami process is the fact that aldehyde substrates containing polar substituents can be successfully employed, a feature exhibited by few other Lewis-acid-catalyzed aldehyde addition reactions. 

In addition to processes involving thioacetate aldols, Mikami has studied the aldol addition reaction of thiopropionate-derived enolsilanes 58, 59 (Eq. (8.14)). The Z-enol silane derived from terr-butyl thiopropionate undergoes addition to benzyloxyacetaldehyde to give products as a 92 8 anti syn mixture of diastereo-mers with the major anti stereoisomer 61 isolated in 90% ee. The additions of E... 

Isotactic vinyl polymers often possess a helical conformation in the solid state however, without bulky substituents present (vide infra) in solution at room temperature, helix—helix reversal takes place fast and no optical activity is observed. Ortiz and Kahn reported a borderline case in which a non-bonded interaction between the monomers leads to the formation of isotactic 39 (Chart 7) by anionic polymerzation at —78 °C. Optically active polymers can be isolated, but in solution the proposed one-handed helicity is lost in less than 1 h.148 An intriguing class of polymers formed by polycondensation of diboronic acid and chiral tetraalcohols has been studied by Mikami and Shinkai and is exemplified by polymer 40 (Chart 7). In this D-mannitol-based polymer, the noncovalent intramolecular interaction between the amines and the boron atoms imposed a sp3-hybridization on boron, which, according to calculations, results in a helical conformation of the macromolecule.149... 

Pressure-jump relaxation was also used by others to study anion adsorption/desorption kinetics on soil constituents. These investigations have included the study of the kinetics and mechanisms of acetic acid adsorption on a silica-alumina surface (Ikeda et al., 1982a) and phosphate (Mikami et al., 1983a) and chromate adsorption (Mikami et al., 1983b), on 7-AI2O3. Double relaxation times on the order of milliseconds were observed in each of these studies. 

G. N. Patwari, T. Ebata, and N. Mikami, Dihydrogen bonded phenol-borane-dimethylamine complex an experimental and theoretical study, J. Chem. Phys. 116, 6056-6063 (2002). 

Based on their early study in the enantioselective carbonyl-ene reaction [23], Nakai, Mikami, and Terada have found that the asymmetric hetero-Diels-Alder reaction of prochiral glyoxylate with methoxydiene can be catalyzed by the chiral titanium complex, producing the a s-dihydropyran carboxylate as a major product in high enantiomeric purity (Scheme 11) [24]. 

Mikami Y, Hata S, Kiyokawa T, et al. Expression of CDIO in malignant miillerian mixed tumors and adenosarcomas An im-munohistochemical study. Mod Pathol. 2002 15 923-930. 

Kaburaki, Y, H. Shigematsn, Y. Mikami, and H. Kusakabe Smdies on the composition of tobacco smoke. XL Relation between vapor phase components and constituents of tobacco (2) Sci. Papers, Cent. Res. Inst., Japan Monopoly Corp. Ill (1969) 143-149. Kaburaki, Y, H. Shigematsn, Y. Yamashita, and H. Kusakabe Studies on the composition of tobacco smoke. XV. Volatile compounds from the neutral fraction of tobacco smoke condensate Agr. Biol. Chem. Japan 35 (1971) 1741-1750. 

The catalysed carbonyl-ene reaction frequently employs reactive aldehydes, especially glyoxalate esters. Mikami s group has studied the titanium/BINOL catalysed carbonyl-ene reaction in considerable detail. Typically, the catalyst is prepared in situ from diisopropoxytitanium dihalide and BINOL in the presence of 4A molecular sieves. Thus, alkenes (7.179) and (7.180) are converted into the homoallylic alcohols (7.181) and (7.182) with high enantioselectivity. Typical examples use up to 10 mol% of catalysts, but variation in the catalyst preparation allows the use of only 0.2 mol%. ... 

H. Saito, J. Mikami, S. Yamaguchi, M. Tanio, A. Kira, T. Arakawa, K. Yamamoto, S. Tuzi, Site-directed solid-state NMR studies on membrane proteins strategy and goals toward revealing conformation and dynamics as illustrated for C-labeled bacteriorhodopsin, Magn. Reson. Chem. 42 (2004) 218—230. 

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