Synthesis of 2-aminoazulene derivatives. Nucleophilic and palladium-catalyzed amination of 2-substituted azulene

Amination of 2-substituted azulene was carefully examined using several types of amines, and the scope and limitation of substrates and reagents in these direct nucleophilic aminations were found. The synthesis of 2-aminoazulenes was successfully achieved by the reaction of 2-bromoazulene with several amines via palladium-catalyzed amination.     

Organic high-spin systems: synthesis, electrochemical and ETSF studies of a series of tetraaryl-meta-phenylenediamines

A series of N,N,N′,N′-tetraaryl-1,3-phenylenediamines with various substituents at the para-position of peripheral rings were designed and synthesized. Electrochemical and novel electron transfer stopped-flow methods were invoked for characterizing the absorption spectra of the corresponding short-lived mono- and dicationic states. Both thermodynamic and kinetic stabilization are required to extend the lifetime of the dicationic states. Useful molecular design rules for stabilizing the dicationic states of N,N,N′,N′-tetraaryl-1,3-phenylenediamines as precursors for positively charged high-spin systems were elucidated.     

Simulation study on microstructure formations in magnetic fluids

We propose the Langevin-type microscopic equations of motion for magnetic fluids. Magnetic fluids are modeled as an ensemble of interacting ferromagnetic nanoparticles suspended in a viscous fluid. The present model is described in terms of position vectors of nanoparticles and orientation vectors of their magnetic dipole moments. In this model, forces and torques arising from the magnetic origin and the surrounding fluid flow are included. Effects of non-spherical particle shape are also taken into account. From the Brownian dynamics simulations of the model, it is found that the present model exhibits various microstructure formation processes in magnetic fluids.     

Explicit solution forp-q duality in two-dimensional quantum gravity

By using Sato's infinite dimensional Grassmannian theory of the KP hierarchy, we study the global structure of the theory space of 2D quantum gravity coupled to various minimal conformal fields labeled by a pair of integers (p, q). After giving a rigorous proof of the equivalence of Douglas's equation and the Schwinger-Dyson equation (W-constrainton a function), we establish thep-q duality of the (p, q) quantum gravity at Green's function level. As an application, we discuss the metamorphosis of operators under unitarity-preserving renormalization group flows.Address after September 1, 1992: Newman Laboratory, Cornell University, Ithaca, NY 14853-5001, USA.     

Quasifinite highest weight modules over the superW 1+∞algebra

We study quasifinite highest weight modules over the supersymmetric extension of theW ₁₊ algebra on the basis of the analysis by Kac and Radul. We find that the quasifiniteness of the modules is again characterized by polynomials, and obtain the differential equations for highest weights. The spectral flow, free field realization over the (B, C)-system, and the embedding into (|) are also presented.Address after April 1, 1994: Research Institute for Mathematical Sciences, Kyoto University, Kyoto 606, JapanAddress after April 1, 1994: Uji Research Center, Yukawa Institute for Theoretical Physics, Kyoto University, Uji 611, Japan     

Total syntheses of (+)-chloropuupehenone and (+)-chloropuupehenol and their analogues and evaluation of their bioactivities

Tetracyclic pyrans (+)-chloropuupehenone (1) and (+)-chloropuupehenol (5) and its C8-R-isomer (+)-3 were synthesized via a one-pot condensation of 1-chloro-2-lithio-3,5,6-tris(tert-butyldimethylsilyloxy)benzene (8) with (4aS,8aS)-3,4,4a,5,6,7,8,8a-octahydro-2,5,5,8a-tetramethylnaphthalene-1-carboxaldehyde (7). The major condensation product, (4aS,6aR,12bS)-2H-9,10-bis(tert-butyldimethylsilyloxy)-11-chloro-1,3,4,4a,5,6,6a,12b-octahydro-4,4,6a,12b-tetramethyl-benzo[a]xanthene (4), after desilylation provided tetracyclic pyran (+)-(4aS,6aR,12bS)-2H-11-chloro-1,3,4,4a,5,6,6a,12b-octahydro-4,4,6a,12b-tetramethyl-benzo[a]xanthene-9,10-diol (3). At a dosage of 42 mg/rat over 8 h, pyran diol 3 inhibited the intestinal absorption of cholesterol by 71% in rats. Tetracyclic pyran 4 was also converted to o-quinone 28, which inhibited cholesteryl ester transfer protein (CETP) activity and L1210 leukemic cell viability with IC(50) values of 31 and 2.4 microM, respectively. Diol (+)-5 inhibited CETP activity with an IC(50) value of 16 microM. The minor condensation product, (4aS,6aS,12bS)-2H-9,10-bis(tert-butyldimethylsilyloxy)-11-chloro-1,3,4,4a,5,6,6a,12b-octahydro-4,4,6a,12b-tetramethyl-benzo[a]xanthene (6), was transformed into (+)-5 and (+)-1. A stepwise stereoselective synthesis of (+)-1 was also developed utilizing an oxyselenylation ring-closure reaction. The synthetic sequence also produced four biologically active naturally occurring drimanic sesquiterpenes, (+)-drimane-8alpha,11-diol (34), (-)-drimenol (38), (+)-albicanol (39), and (-)-albicanal (31) as intermediates.     

Conformation of 2-aminomethylpyrrolidine and 2-aminomethylpiperidine in ternary platinum(II) complexes: regulation of conformation of the diamine by the coexisting ligand

Square-planar complexes with the formula [Pt(L(2))(L(1))](X)(2) x nH(2)O, where L(1) is S-2-aminomethylpyrrolidine (S-pyrda) or 2-aminomethylpiperidine (pipda) and L(2) is diammine (X=Cl), cyclobutane-1,1-dicarboxylato (cbdca) (X=none), 2,2'-bipyridine (bpy) (X=NO(3)), or 1,10-phenanthroline (phen) (X=Cl), were prepared and the nature of the coordination of L(1) was examined by (1)H-NMR spectroscopy and X-ray crystallography. These 2-aminomethylazacycloalkane derivatives form five-membered chelate rings condensed with an azacycloalkane ring in cis- or trans-configurations. The (1)H-NMR spectrum of complexes with S-pyrda as L(1) were consistent with cis-condensed rings in an S(N) conformation with any of L(2) group. However, (1)H-NMR spectra of the complexes with pipda as L(1) indicated trans-fused successive rings for the diammine and cbdca as L(2), but spectra for bpy and phen as L(2) were consistent with a conformation having cis-fused successive rings. X-Ray crystallography data for the two complexes with pipda as L(1) and cbdca (1) and bpy (2) as L(2) confirms the different coordination behavior in the solid state.     

Synthesis of high surface area hydroxyapatite nanoparticles by mixed surfactant-mediated approach

A new surfactant-mediated approach was developed to synthesize hydroxyapatite (HAp) nanoparticles with high surface areas by calcination of their precursors encapsulated with calcium stearate using mixed surfactant-containing reaction mixtures. Acidic aqueous solution of calcium phosphate was mixed with both or either nonaoxyethylene dodecyl ether (C12EO9) and polyoxyethylene(20) sorbitan monostearate (Tween 60) and then was treated with aqueous ammonium at 25 degrees C. The C12EO9-based single surfactant system yielded an aggregate of platy HAp nanoparticles 20-40 nm in size, whereas the Tween 60-based single and mixed systems led to lath-shaped HAp nanoparticles 2-8 nm wide and encapsulated with calcium stearate. On calcination at 500 degrees C, the stearate-encapsulated HAp nanoparticles in the latter two systems were deorganized into high surface area HAp nanoparticles. Particularly, the HAp nanoparticles in the mixed system exhibited a specific surface area as high as 364 m2 g(-1) that is roughly 3 times larger than 160 m2 g(-1) for those in the single system. The significantly high surface area for the former is attributed to much less adhesion of decapsulated HAp nanoparticles, which originated from the particle-separating effect of the C12EO9 molecules adsorbed on the outer surface of the stearate-encapsulated HAp nanoparticles to inhibit their agglomeration or interfacial coordination. The present results demonstrate that the mixed use of two different surfactants as a source of encapsulating and templating agent and a particle-separating agent is specifically effective for the synthesis of high surface area HAp nanoparticles.     

Diastereoselective intermolecular radical addition to nitrones

The intermolecular radical addition to chiral nitrones 2, 4, 5, and 16 was studied. The isopropyl radical addition to Oppolzer's camphorsultam derivative 2 of glyoxylic nitrone proceeded with excellent diastereoselectivity to give the desired isopropylated product 3a accompanied by the diisopropylated product 3b. A high degree of stereocontrol in the reaction of cyclic nitrone 4 was achieved. The ethyl radical addition to nitrone 4 with triethylborane afforded the desired ethylated product 9a accompanied by the diethylated product 10a and the ethylated nitrone 11a. To evaluate the utility of cyclic nitrone 4, several alkyl radicals were employed in the addition reaction, which afforded the alkylated products 9b-d with excellent diastereoselectivities. In the presence of Mg(ClO(4))(2), the ethyl radical addition to BIGN 16 afforded selectively syn isomers. In contrast, the alkyl radical addition to 16 took place even in the absence of Lewis acid to give anti isomers.     

A novel synthesis of amino-1,2-oxazinones as a versatile synthon for beta-amino acid derivatives

The radical addition-cyclisation of alpha, beta-unsaturated hydroxamates containing an oxime ether provides a novel method for the stereoselective synthesis of amino-1,2-oxazinones. Its synthetic utility is demonstrated by a stereoselective synthesis of beta-amino acid derivatives, such as alpha-alkyl-beta-amino-gamma-lactone and alpha,beta-disubstituted beta-lactam.