Radical [3 + 2] cycloaddition reaction with various alkenes using iodomethylcyclopropane derivatives as new homoallyl radical precursors

Radical iodine atom transfer [3 + 2] cycloaddition with various alkenes using dimethyl 2-(iodomethyl)cyclopropane-1,1-dicarboxylate and 1,1-bis(phenylsulfonyl)-2-(iodomethyl)cyclopropane as new precursors of a homoallyl radical species smoothly proceeds to give functionalized cyclopentane derivatives in good yields.     

Oxidation of allylic alcohols, amines, and sulfides mediated by assembled triphase catalyst of phosphotungstate and non-cross-linked amphiphilic copolymer

A novel catalyst PWAA, an assembled complex of phosphotungstic acid (H₃PW₁₂O₄₀) and a non-cross-linked copolymer of N-isopropylacrylamide with an ammonium, was developed. It is an amphiphilic, cross-linked, and supramolecular insoluble complex and showed catalytic activity on oxidation with aqueous hydrogen peroxide. PWAA, used in 2.7×10⁻⁵-2.0×10⁻³ mol equiv., catalyzed oxidation of allylic alcohols, amines, and sulfides efficiently. The turnover number (TON) of PWAA reached up to 35,000. PWAA showed a good stability in organic/aqueous media and was reused three to five times.     

Carbonyl methylenation of easily enolizable ketones

An organometallic reagent prepared from CH₂I₂, Zn, and TiCl₄ is effective for methylenation of the title ketones.     

Cation-pi interactions of a thiocarbonyl group and a carbonyl group with a pyridinium nucleus

Attractive interactions between a thiocarbonyl group and a pyridinium nucleus, and between a carbonyl group and a pyridinium nucleus have been proven by (1)H and (13)C NMR studies, UV-vis spectral analyses, and X-ray crystallographic analyses of nicotinic amides 1 and 3, and pyridinium salts 2 and 4. Comparison of the Deltadelta values, which are the differences in the chemical shifts with reference compounds 5 or 6, showed that the absolute Deltadelta values of 2 and 4 are much larger than those of 1 and 3. In the UV-vis spectra, the n-->pi absorption of the C=S group of 2a exhibited a significant blue shift in CHCl(3). X-ray crystallographic analysis of 1-4 clearly showed that the C=S group of 2a and the C=O group of 4 are very close to the pyridinium moiety compared to the case of 1 and 3. In addition, the X-ray crystal packing structure of 2a showed the C=S group is sandwiched between two pyridinium rings. These experimental results strongly suggested the existence of attractive (C=S)...Py(+) and (C=O)...Py(+) interactions in solution and in crystal. The optimized geometries of 1 and 2 calculated at the HF/6-311G level are in good agreement with their X-ray geometries. MP2/6-311G calculations for the model systems of pyridinium salts 2 and 4 predicted that the electrostatic and induction energies are the major source of the attractive interactions. Since the larger contribution of electrostatic and induction interactions are characteristic features of cation-pi interactions, the (C=S)...Py(+) and (C=O)...Py(+) interactions would be classified as a cation-pi interaction.     

Deuterium relaxation time ofα-d-tryptophan included in cyclodextrin host molecules

Deuterium relaxation times ofd- andl--d-tryptophan included in -cyclodextrin derivatives were directly measured by deuterium NMR spectroscopy. The results showed that the molecular motion of the tryptophan molecule was strongly restricted even in the cavity of unmodified -cyclodextrin and the additional recognition groupings — ammonium and carboxylate — on -cyclodextrin did not affect the molecular motion of tryptophan, though the association constants were significantly enhanced.Deceased on March 22, 1987.     

Diversity-oriented synthesis of tamoxifen-type tetrasubstituted olefins

A general synthetic scheme for tamoxifen-type tetrasubstituted olefins based on the novel Cu-catalyzed carbomagnesation across alkynyl(2-pyridyl)silane has been developed. A wide array of electronically and structurally diverse tetrasubstituted olefins can be prepared in a regiocontrolled, stereocontrolled, and diversity-oriented manner. Noteworthy features are that (i) the three aryl groups, which are believed to be important (essential) for anti-estrogenic activity, can be varied at will because they all stem from readily available aryl iodides, and (ii) any stereo- and regioisomers can, in principle, be prepared by simply changing the applying order of aryl iodides into the sequence.     

Structures and conformations of metabolites of antitumor cyclic hexapeptides, RA-VII and RA-X.

Metabolites of antitumor cyclic hexapeptides, RA-VII and -X which were isolated from Rubia cordifolia were studied by hepatic microsomal biotransformation in rats and in bile juice of rabbits to which these drugs were administered intravascularly. Their structures and conformations were elucidated by two-dimensional nuclear magnetic resonance techniques, temperature effect on NH protons and nuclear Overhauser effect experiments. Specific N-demethylation of Tyr-3, O-demethylation and hydroxylation at aromatic rings of Tyr-3 and -5 were observed. Compared with metabolites of RA-VII, most of RA-X was excreted unchanged in the bile juice. Relationship among their structures, conformations and antitumor activities is also discussed.     

Chiral ligand-controlled asymmetric conjugate addition of lithium amides to enoates

The external chiral ligand-controlled asymmetric conjugate addition reaction of lithium amides with alpha,beta-unsaturated esters provided beta-amino esters in high yields and high enantioselectivities.     

In Situ Processing of Nano Crystalline Oxide Particles/Polymer Hybrid

Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO₃/, PbTiO₃/, and KNbO₃/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior.     

Manipulation of droplets by dynamically controlled wetting gradients

The reversible transportation of droplets was realized by spatiotemporal control of the wetting gradient. The surface wetting was reversibly regulated by using electrochemical reactions of the ferrocenyl (Fc) alkanethiol monolayer, and the wetting gradient was generated by the application of the in-plane bias voltage to the substrate. The back-and-forth motion of the wetting boundary, where the surface changed from wetting to repulsive, sequentially caused a droplet unidirectional spreading and shrinking on the surface. These unidirectional deformations resulted in the net transport of the droplet in an inchwormlike manner. The droplet moved backward when the direction of the in-plane bias voltage was reversed.