We have already reported the synthesis, properties, and redox behavior of stable ferrocenyldiphosphenes as novel d-pi electron conjugated systems containing heavier main group elements. We have designed a new type of bulky ferrocenyl units and applied them to the synthesis of a novel 1,2-bis(ferrocenyl)diphosphene derivative. As a result, 1,3-Ar₂-2-iodoferrocene (Ar = 3,5-dimethylphenyl or 3,5-di-t-butylphenyl) was successfully synthesized as bulky ferrocenyl units. Finally, 1,2-bis(ferrocenyl)diphosphene derivative bearing the bulky ferrocenyl units was synthesized and isolated as a red-purple crystalline compound. Physical and chemical properties of this 1,2-bis(ferrocenyl)diphosphene will also be described.

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It is well known that Tetrathiafulvalene (TTF) is most popular donor component of molecular conductor. The appearance of metallic conductivity in cation radical salt of TTF requires intrastacked mixed valence interaction. Investigation of oligo-TTF units contributes to understand face-to-face interaction between the TTF units. Thus, we report the synthesis and properties of TTF oligomer with flexible alkylenedithio linker.

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Cyclooctatetraene (COT), a 8pi cyclic conjugated ring skeleton, is an attractive framework because of its dynamic motion, namely tub-to-tub inversion in solution, as well as its good stability in redox processes. In this study, we designed and synthesized a cyclic thiazole tetramer that has the COT framework at the center of the molecule. In this skeleton, pi-conjugation of the flexible COT framework is extended in four directions. The crystal structures and electrochemical properties for a series of the COT derivatives will be described.

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Thiophene-containing polycyclic compounds (heteroarene) have been attracting a great deal of interest in view of application to organic semiconducting materials for electronic device applications, such as organic field-effect transistors (OFETs). Among them, acenedithiophenes represented by benzodithiophene (BDT) and anthradithiophene (ADT), where two thiophene rings are fused on a benzene and an anthrathene core, respectively, demonstrate the usefulness of this class of compounds. In contrast, naphthodithiophenes (NDTs), where two thiophene rings are fused on a naphthalene core, have been scarcely investigated because of the lack of suitable synthetic method. In this contribution, we report the synthesis and characterization of the linear-shaped NDT derivatives, i.e., naphtho[2,3-b:6,7-b']dithiophenes and naphtho[2,3-b:7,6-b']dithiophenes and the angular-shaped NDT derivatives, i.e., naphtho[1,2-b:5,6-b']dithiophenes and naphtho[2,1-b:6,5-b']dithiophenes.

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Oligothiophenes containing dioxocyclopenta[c]thiophene bearing bulky bis(di-t-butylphenyl) groups , or cyclopenta[c]thiophene bearing sterically compact fluorene moiety were designed and synthesized towards insulated molecular wires to investigate single-molecule conductance. The photophysical and electrochemical properties as well as the encapsulation effect of these oligomers were investigated. The measurement of the single-molecule conductance was carried out using modified STM techniques.

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Mechanochromism is the phenomenon when crystals undergo a major change of color due to mechanical stimuli. Because of recent emerging development of mechanoresponsive materials, such as polymeric materials doped with dyes, and fluorochromic liquid crystals induced by shear-stress, the discovery and development of molecules which respond in a productive fashion to mechanical stimuli ("mechanophores") is an important aspect in this area. We have been studying bis(spirodienone)-bridged bithiophenes, which are new building block for redox-active molecular switching materials. We recently found that N,N-dialkylaminophenyl-substituted-2,2'-bis(spirodienone)-bridged-3,3'-bithiophenes act as new mechanopheres. During grinding the crystals, the color was changed from yellow to reddish orange, and the reddish-orange color was immediately turned back to yellow by exposure to organic solvents. On the basis of solid-state UV-Vis and ESR spectra, X-ray powder diffraction, the observed mechanochromism is found to cooperate an intramolecular bond-breaking/forming with a switching between crystalline and amorphous states.

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We discovered that the click reaction of doubly ortho-substituted aromatic azide with alkyne proceeds faster than that of unsubstituted phenyl azide, inspite of the steric hindrance. The kinetic study of click reaction using various azides has shown clear relationship between bulkiness of the substituents and the reaction rate. Along with the results of spectroscopic analyses and density functional theory (DFT) calculations, we will discuss the accelerating effect elicited by the bulky substituents of aromatic azide in the click reaction.

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Formation of benzyl cation by the irradiation of 2-benzyloxy-naphthalene (1a), 3-hydroxy-2-benzyloxy- naphthalene (1b), and 2'-hydroxy-2-benzyloxy-1,1'-binaphthalene (1c) were investigated in MeOH and in TFE. Irradiation of 1a afforded benzyl alcohol as a major product, indicating O-CH2 bond homolysis in its excited state. The irradiation of 1b, on the other hand, afforded benzyl methyl ether, which is derived by the nucleophilic addition of solvent to benzyl cation. An intramolecular hydrogen bonding or photoacidic catalysis of 3-OH to the benzyl ether oxygen may be responsible for the O-CH2 bond heterolysis, while irradiation of 1c, of which structure could exhibit intramolecular hydrogen bondings, did not afforded any O-CH2 bond heterolysis product. The reaction mechanisms will be discussed based on the ab initio MO calculation of their excited states.

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We successfully synthesized various enantiomerically pure P-stereogenic diphosphacrowns. They are the first example of the stereo-controlled synthesis of crown ether derivatives containing chiral hetero atoms. Additionally, their transition metal complexes were synthesized and utilized as asymmetric catalysts. The structures of diphosphacrowns obtained and the effect of their ring size on the reaction will be reported in detail.

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A difluorovinyl group has been introduced into a variety of organic compounds as a useful functional group, and widely used in the fields of medicinal chemistry, agricultural chemistry, and materials science. Although 2,2-difluorovinylzinc chloride was considered a promising reagent for coupling reactions to introduce the difluorovinyl group, its insufficient thermal stability resulted in low yields of the coupling products. We thus have prepared thermally stable 2,2-difluorovinylzinc chloride-N,N,N',N'-tetramethylethylenediamine (TMEDA) complex, and succeeded in synthesizing various types of 1,1-difluoroalkenes via its cross-coupling reactions with organohalides.

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Cyclic polymers are interested in their low melting points, viscosity, etc, in comparison with their corresponding linear chain analogue. On the other hand, physical properties of cyclic polymers have not been investigated widely, because efficient synthetic methods have not been developed. We designed and prepared novel precursor, having two reaction points derived from nitroxide-based diradical, for ring-expansion polymerization of polyolefines. As the result, we succeeded to prepare ring polystylenes using these new precursors. The details of reaction will be discussed with GPS, MALDI-TOF-MS, and some other spectroscopic data.

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Reaction of alkene with hypervalent iodine gave a dioxolanyl cation intermediate, which reacts regioselectively with various nucleophiles to yield highly stereoselective oxidation products.

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The investigation of the behavior of ion pair intermediates generated in solvolysis reaction is one of the subjects of continuing interest. There are two type carbocations with which the benzene ring interacts. One is the benzylic carbocation, and the other is the phenonium ion. The solvolysis of 2-Phenylethyl tosylates having strongly electron releasing substituents proceeds by phenyl assisted mechanism via phenonium ion intermediate. We are interesting in the behavior of ion pair intermediate including phenonium ion. Therefore, we are investigating the solvolysis of 4-MeO and 4-Me ring substituted 2-phenylethyl tosylate in 50/50 (v/v) Trifluoroethanol/H₂O (I = 0.5, NaClO₄). We will discuss the solvolysis mechanism of 2-phenylethyl tosylates based on the effect of the added nucleophile and the distribution of products during solvolysis.

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Reactions via carbocationic intermediates and reaction integration in [BMIM] ionic liquids were investigated. The rate constants for solvolysis of 2-adamantyl p-toluenesulfonate in ionic liquid [BMIM][BF₄] were found to be similar to those in ethanol. Dediazoniation of substituted benzoylbenzenediazonium salts in [BMIM][Tf₂N] and [BMIM][TfO] gave fluorenones as main products, which could be formed by radical mechanism. Furthermore, reaction integration with Sonogashira coupling, desilylation, and subsequent Sonogashira coupling of iodobenzophenone, trimethylsilylacetylene, and triiodobenzene in [BMIM][Tf₂N] successfully gave a dendrimeric product.

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Computational Studies with have been carried out for a series of aliphatic and aromatic olefin radical cations and the corresponding peroxy radical cations that are formed by the reactions of the olefin radical cations with molecular oxygen. Careful analyses of the structures, the positive charges, and the spin distribution obtained have shown that the delocalization of the positive charge plays an important role in the stability of the peroxy radical cations.

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Theoretical study on Keto-Enol Tautomerism using QM/MC/FEP method.

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Stabilities of aromatic cations are governed by inductive and resonance effects of ring substituents, which are well described by the Yukawa-Tsuno equation. On the other hand, LFER for anionic systems has not yet been established due to experimental difficulties. Recently, we introduced theoretical method to investigate anions. In the preceding symposiums, we reported that the stabilities of benzylic anions and phenylamide anions are governed by inductive, resonance, and saturation effects, and an extended Yukawa-Tsuno equation was proposed for these anionic systems. In order to establish generality of this equation, more extensive analyses on various anionic species are desirable. In this point of view, we extended this type of research to phenoxide ions. We used proton transfer equilibria to determine the relative gas phase stabilities of ring substituted phenoxide ions. Energies of species in these equilibria were calculated by means of DFT method. We compared substituent effects of phenoxide ion with various benzylic anions. Detailed statistical analyses confirmed that an extended Yukawa-Tsuno equation reported is also necessary to describe substituent effects of phenoxide ion.

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Self-propelled oil droplets have drawn much attention as a primitive type of inanimate chemical machinery in an aqueous surfactant solution, that is, the energy transduction from chemical energy to mechanical energy. Here, in order to investigate and regulate the self-propelled motion of droplets, we have synthesized the cationic surfactants containing ester linkages as the hydrolysable moiety depending on pH. Also, we explored the possibility that cationic surfactant systems demonstrate the movement of oil droplets. As systematical exploration of the components of oil droplets, we have found that alkyloxybenzaldehyde oil droplets show self-propelled motion reproducibly in the solution of cationic surfactant. It was also observed in the basic media that oil droplets moved with the evolution of the aggregation containing water and oil phases. Moreover, the duration of the self-propelled oil droplets in basic media was longer than that in acidic media. These results may be due to the production of a carboxylate-type anionic surfactant and a quaternary ammonium alcohol caused by the hydrolysis of the ester-containing cationic surfactant.

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Ambident anion which has two nucleophilic O and C sites gives the O-attack and the C-attack product by a reaction with an electrophile. In this study, methylation of phenylmethylnitronate was investigated experimentally by kinetic measurement with a UV spectrometer. The results were compared with theoretical calculations for the reactions of nitronate anions with electrophiles and experimental results for nitoalkane anomaly on proton transfers of phenylnitromethanes.

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The reaction of N-sulfinylimines with allylmetal reagents are known to proceed via a cyclic transition state to show high stereoselectivity. On the other hand, activation of the reaction via a previously difficult acyclic transition state was realized by using TMSOTf as a Lewis acid in the reaction with a pentadienyltin reagent which is known to show the regioselectivity corresponding to the reaction pathways. Reactions of N-sulfinylimines with other allyltins and silyl enolates will be also reported.

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Asymmetric oxidation of thioanisole with hydrogen peroxide in MeOH using (R)-MOF as catalyst. An optically active (R)-methyl phenyl sulfoxide was obtained in 38% yield and 55% ee.

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In this research, we investigated the enantioselective synthesis of helically chiral 1,1'-bitriphenylenes by the double [2+2+2] cycloaddition of biaryl-linked tetraynes with carbonyl-linked 1,4-diynes. As a result, we were pleased to find that the desired cycloaddition reaction proceeds at room temperature to yield the desired 1,1'-bitriphenylenes with good yields and high ee values by using cationic rhodium(I)/BINAP-type bisphosphine complexes as catalysts.

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Recently, we have discovered the significantly enhanced clickability of doubly sterically-hindered aryl azides. In this poster presentation will be discussed the differences in reactivity among various azides in metal-catalyzed or metal-free click reactions to develop sequential multi-click reaction by discriminating the the type of azido groups. Our study has shown that sterically-hindered aromatic azido group remains almost intact in Ru-catalyzed cycloaddition with an alkyne. Futhermore, the difference in reactivity between aromatic and aryl azides has been examined in detail.

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I developed synthetic method of pyromellitic diimide-based macrocycles by using flow micro reactor. Synthesis of pyromellitic diimide-based macrocycles by conventional flask reactions using high dilution method resulted in the formation of the desired macrocycles in low yield. In this work, I synthesized the macrocycle by using flow microreactor in higher yield and size-selectivity.

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Photocatalytic fluorination of benzene by F^- occurs under UV-light irradiation of an O₂-saturated acetonitrile solution containing 3-cyano-1-methylquinolinium ion (QuCN⁺) and TEAF4HF to yield fluorobenzene and hydrogen peroxide. The photocatalytic reaction is initiated by electron transfer from benzene to the singlet excited state of quinolinium ion followed by addition of F^- to benzene radical cation.

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Biselides A-E were isolated from the Okinawan ascidian by our group. Biselides A and B showed cytotoxic activities against various human cancer cell lines. Recently, we achieved the total synthesis of haterumalides NA and B, which are analogues of biselides. We planned to synthesize biselides A, B and E from a common intermediate of haterumalides. In here, we report synthetic study of biselides by using the regioselective allylic oxidation or the lipase-catalyzed deacetylation to introduce hydroxy group at C20 position of biselides.

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Oxylactonization of ortho-alkenylbenzoate by conventional oxidizing reagents preferentially gave a gamma-lactone product, while the oxidation with hypervalent iodine reagent selectively gave a delta-lactone product. Asymmetric synthesis of bioactive natural products, 4-oxyisochromanones was achieved using hypervalent iodine.

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Ionic liquids have attracted attention for application in organic synthesis. We successfully synthesized dendrimer-based trisketon from 4-iodobenzophenone derivative and trimethylsilylacetylene by 3 step integrated reaction (Sonogashira coupling reaction, deprotection and Sonogashira coupling reaction with 1,3,5-triiodobenzene) in an imidazolium-based ionic liquid, [BMIM][Tf₂N]. A similar integrated reaction with dihalogenated benzophenone in [BMIM][BF₄] or [BMIM][Tf₂N] was under investigation.

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Intramolecular radical cyclizations of 1,1-difluoroalkenes possessing a bromoaryl group were examined. By the aid of the high reactivity of the intermediary aryl radicals, the intramolecular radical cyclization manner. Using this reaction, we have accomplished the construction of nitrogen-,readily proceeded in a 5-exo-trig oxygen-, or sulfur-containing five-membered heterocyclic rings bearing a difluoromethyl group.

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A new hydroxyamide-functionalized N-heterocyclic carbene (NHC) ligand was designed. Asymmetric reaction of cyclic enone with Et₂Zn catalyzed by Cu(OTf)₂ in the presence of the NHC precursor azolium took place to give the corresponding conjugate addition product. It was found that the reversal of enantioselectivity was achieved when the reaction was carried out by using Cu(acac)₂ combined with the same ligand precursor.

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Recently, we succeed in developing hydroxy-amide-functionalized azolium compound as N-heterocyclic carbene (NHC) precursor. Now, a new NHC-Ir complex was synthesized by using the azolium salt derived from chiral .beta.-aminoalcohol. Azolium salt was converted into the NHC-Ag complex, which subsequently reacted with [IrCp*Cl₂]₂ to form the NHC-Ir complex whose structure was characterized by X-ray crystallographic studies. The Ir complex thus obtained catalyzed asymmetric transfer hydrogenation of acetophenone by 2-propanol to give the corresponding sec-alcohol in 60% ee.

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Phenacyl chlorides react with methoxide ion to afford acetal as the main product and ether as a by-product. It was considered that the acetal was obtained by the nucleophilic attack on the carbonyl carbon by the methoxide ion and a ring opening reaction of the epoxy intermediate and that the ether was obtained by the SN2 substitution reaction. The purpose of this study is to analyze the reaction mechanism on the basis of the effect of substituent on the product ratio and the reaction rate and the influence of the concentration of the methoxide ion on the reaction rate.

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It was not observed that free energies of activation for the reaction between piperazine and benzyl bromide were highly dependent on solvent polarity. For example, the difference of activation free energies in i-butanol and formamide in 303K was measured to be 0.8kcal mol^-1 although the dielectric constant of the alcohol differs by 93.0 from that of the amide. In contrast, a large difference (17.0kcal mol^-1) of activation free energies in those solvents were calculated using QM/MC/FEP calculation although the calculated activation free energies for i-BuOH is coincident with that observed (21.3 and 20.8 kcal mol^-1). In this study, we tried to reproduce the observe tendency by including a solvent effect to piperazine.

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Acyloin (R₁COCH(OH)R₂) and its derivatives react via intramolecular double proton transfer. Previous MO calculations have shown that this proton transfer had two types of transition states (TSs), one with proton transfer occurring ahead of hydride transfer and the other with the reverse situation. When R₁ = R₂, the two TSs are identical, and thus the reaction should go through the two TSs equally. However, it is unclear whether the same is true with dynamics effect. But, if this theory works with dynamics effect is unclear. The results of theoretical analyses will be reported.

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To prepare organoboron compounds bearing boron-carbon bonds with unique electronic states, novel dichloroborane having a pincer ligand was synthesized. It was then treated with silver trifluoromethanesulfonate to provide bis(trifluoromethanesulfonyl)borane with considerably covalent boron-oxygen bonds, as evidenced by its X-ray diffraction analysis. The dichloroborane reacted with silver tetrafluoroborate to provide the unexpected borenium ion. Reaction of the dichloroborane with potassium graphite provided an unexpected boron compound.

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Azobenzene has extensively been studied as a photo-functional dye. The increase of the molecular extinction coefficient of azobenzene leads to highly photo-sensitive materials. In this study, we synthesized various silyl-substituted azobenzenes and found that the molecular extinction coefficients of these compounds are much larger than that of azobenzene. We discuss these results on the basis of theoretical calculations of molecular orbitals and transition moments.

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A silicon analog of hipposudoric acid (3,7-di-tert-butyl-5,5-dimethyl-1H-dibenzo[b,d]silole-1,4,6,9(5H)-tetraone) and some related compounds are synthesized. This compound has a silole ring fused with two quinone rings. Because of the structure, their carbonyl groups are forced to close to each other and the molecule has a highly distorted non-planar pi-conjugation system. Redox potentials and electronic absorption as well as photoreactivities of the compounds will be discussed.

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Tetrahedrane is one of the most strained organic molecule containing four cyclopropane rings in fused system. Recently, we succeeded in synthesizing a variety of tetrahedrane derivatives. Functionalization of tetrahedranes can be achieved by substitution of tetrahedranyllithium. Now we develop the new versatile, and general synthetic method of aryl-substituted tetrahedranes by employing palladium-catalized cross coupling reaction.

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Stable 1,2-dihydrodisilenes were synthesized by using steric protection groups. The structures of the 1,2-dihydrodisilenes were elucidated on the basis of NMR, UV-vis, IR, and Raman spectra as well as X-ray crystallographic analysis. The s-character of the Si-H bonds of the 1,2-dihydrodisilenes was increased compared to those of ordinary hydrosilanes. Thermolysis of the 1,2-dihydrodisilenes resulted in isomerization to cyclized disilanes. The reaction mechanism of this thermal isomerization was investigated with the aid of theoretical calculations, revealing the intermediacy of silylsilylenes generated by [1,2]-hydrogen shifts of the 1,2-dihydrodisilenes.

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Recently, we reported the synthesis and structure of the first stable Group 4 silylene complexes which bicyclic ligand. Such novel coordination compounds were classified as Shrock-type silylene complexes, based on their reactivity forward methanol and supported by calculations. Herein, we report the reactivity of Group 4 silylene complexes forward alkynes and isocyanides.

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We have reported the synthesis of fused bicyclic disilene (bicyclo[3.3.0]octasila-1(5)-ene) 1 and revealed that the Si=Si bond of 1 is slightly cis-bent. In order to synthesize a remarkably cis-bent fused bicyclic disilene, we prepared new disilenes (cis-3 and trans-3) with functionalizable phenyl groups at 3- and 7-positions. Molecular structures and reactions of cis-3 and trans-3 will be discussed.

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Radialenes are cross-conjugated cyclic compounds and known to have unique electronic structures. We have succeeded in the synthesis of the first stable triphospha[3]radialene 1, where the three exo-carbon atoms of the [3]radialene skeleton were all replaced by phosphorus atoms. The molecular structure of 1 was revealed by spectroscopic and X-ray crystallographic analyses. In the crystal structure of 1, three phosphorus-carbon bond length of the central framework are within the typical range for those of phosphaalkenes, indicating their double-bond character. The absorption spectrum of 1 showed a strong absorption in the longer wavelength range (absorption maximum = 526 nm, molar extinction coefficient = 1.92 X 10⁴) than those of [3]radialenes. This result strongly suggested the conjugation of the P=C double bonds of 1. The details of electronic structure of 1 will be discussed based on the experimental results and theoretical calculations.

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In order to determine the most stable structure of hexacoordinated phosphates bearing either two Martin-Ligands or two extended Martin-Ligand, phosphoranes which have an alkyl mono-dentate with two phenyl groups at the beta position were synthesized and reacted with base. The 31P NMR measurements of the reactions showed that only one hexacoordinated phosphate isomer is formed for the extended Martin-Ligand system while two are formed for the Martin-Ligand system. The structures of the hexacoordinated phosphates were established on the basis of X-ray crystallographic analysis. It is indicated that the mechanism of the formation of most stable structure is different between the two systems.

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Bowl-shaped phosphorus compounds with large substituent groups are utilized for unique metal-complexes and catalytic reactions. In this study, we focused attention on anthracene as a large aromatic panel and synthesized novel tribranched phosphorus compounds providing three or six anthracene panels. The structures were confirmed by NMR and MALDI-TOF MS analyses. We revealed the spectroscopic properties and reactivity of the anthracene trimer and hexamer.

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The relativistic effect on absolute magnetic shielding tensors (sigma(S) and sigma(Te)) was evaluated for various sulfur and tellurium species (40 species for each) with the DFT(BLYP)-GIAO method, in relation to that on sigma(Se). The relativistic effect on sigma(S), sigma(Se), and sigma(Te) were analyzed as the series of group 16 element. The results will be presented in the viewpoint of similarities and differences.

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In the present study, it aimed to synthesize a series of diferrocenylbithiophenes with one or more methyl groups, and to discuss the relation between those electron states in oxidated states and the steric hindrance by methyl groups.Consequentially, each compound showed different electron states.These results show that the steric hindrance by substituents is important for constructing compound that can transmit information.Moreover, we compared experimental data with theoretical data that were obtained with Gaussian09.

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Our group has been elaborating [14]triphyrins(2.1.1) by using Lindsey method or McMurry coupling method. However triphyrins with thiophene skeleton have not been reported until now. Therefore in this work, one of pyrroles of triphyrin had been changed to thiophene and formylated, then cyclized by McMurry coupling method to get thiatriphyrin. However we got thiatriphyrin analogues that was nonaromatic. The synthesis and photophysical properties of the products were investigated.

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Because of unstability of sulfenic acid the reactivity of sulfenic acids has been unexplored. Therefore, in order to clarify the most basic characters of sulfenic acid, kinetic investigation for the model reaction of selfcondensation was carried out under general acidic and basic conditions using 1-anthraquinonesulfenic acid and substituted methyl benzenesulfenates. The kinetic behavior was found to involve both specific base and general base.

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We report here the synthesis and properties of stable enethiols 2 derived from 2-adamantylthioketones 1 carrying an alpha-hydrogen. Synthesis of thiones 1 was performed by reaction of the corresponding hydrazones with S2Cl2. The proton abstraction reaction of 1 with KH easily proceeded to give the corresponding enethiolates. Quenching of the reaction mixture gave the thermally stable enethiols 2. The synthesis and characterization of 2-adamantylthioketones as well as the observation of tautomerization of 1 will be discussed.

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We designed new donor molecules which show the new function such as reproducible conductivity with electrical switching ability responded to the external stimuli and absorptive ability into titanium oxide. 4,5-Diazafluorene derivatives which exhibit high coordination ability with various metal ions are one of the best candidates for the study of the relationship between electrical conductivities and molecular orientation of the donor molecules in the crystals. We synthesized new metal-coordinated donors (1) incorporating a 4,5-diazafluorene moiety as a metal binding site and a crown ether unit as another metal binding site. 1 was obtained in moderate yields (28-50%) by cross-coupling reaction of 4,5-diazafluoren-9-one with corresponding crown ether derivatives. Syntheses of new donors, polypydidine ruthenium complexes and the results of their electrochemical and spectral properties will be discussed in detail.

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