The first synthesis of (±)-brevione B, an allelopathic agent isolated from Penicillium sp.

Breviones A∼E (1∼5), allelopathic agents isolated from Penicillium brevicompactum Dierckx, are structurally unique pentacyclic or hexacyclic diterpenoid derivatives. The first synthesis of brevione B (2) was achieved by employing the double S_N2′-type tandem reaction as a key step.     

Conductive characteristics of radical‐bearing polythiophenes using a microcomb‐shaped electrode

The electric conductivity of π‐conjugated and radical‐bearing polymers, i.e., polythiophenes bearing pendant galvinoxyl and phenoxyl radical groups, was measured using a microcomb‐shaped electrode. The electric conductivity was found to be enhanced by the radical content in the polymer. The infrared (IR) and Raman spectroscopies suggested a structural change from an aromatic form to a quinoid one in the polythiophene backbone by the phenoxyl radical generation. The effect of the pendant galvinoxyl radical's unpaired electron on the electric conductivity of the polythiophene was discussed by comparing the conductivity of a radical‐bearing polystyrene and a polythiophene mixed with low‐molecular radical molecules. Copyright © 2007 John Wiley & Sons, Ltd.     

Development of Odorless Thiols and Sulfides and Their Applications to Organic Synthesis

Summary. Development of new odorless thiols (dodecanethiol, 4-n-heptylphenylmethanethiol, 4-trimethylsilylphenylmethanethiol, 4-trimethylsilylbenzenethiol) and an odorless sulfide (1-methylsulfanyldodecane) and their applications to dealkylation, Michael addition, Swern oxidation, and Corey-Kim oxidation are described.     

Preparation of Silica-Silk Fibroin-Polyurethane Composite Films via a Sol-Gel Route

A tetraethoxysilane (TEOS)-derived sol aged for 0 h–6 h at room temperature was mixed with a polyurethane (PU) matrix. A composite of silk fibroin (SF) powders and acrylamide (AAm) was dispersed in the sol-PU mixture and dried isothermally at temperatures between 25°C and 120°C to obtain composite films. Three competitive reactions take place, i.e., those between silica-silica, SF-PU and silica-organic phases, during formation of the composite films. These reactions determine the properties such as morphology and homogeneity of the composite films. IR absorption bands for amide groups (–CONH–), C=O (amide I, 1730 cm^–1) and N–H (amide II, 1530 cm^–1) become larger with decreasing aging time of TEOS-derived sol, or increasing drying temperature. DTA exothermic peak due to the thermal decomposition of SF-AAm composite, on the composite films prepared from the 0 h-aged sol or dried at more than 50°C, shifts toward higher temperature by 44 K or more than 63 K respectively, as compared to the SF-AAm composite. Shorter aging time of TEOS-derived sol and higher drying temperature increased the extent of dispersibility, among SF-AAm composite, PU and silica, to bring a composite film more homogeneous.     

BINAP/AgOTf/KF/18-crown-6 as new bifunctional catalysts for asymmetric Sakurai-Hosomi allylation and Mukaiyama aldol reaction

A catalytic amount of KF.18-crown-6 complex is effective as a soluble fluoride source to activate an asymmetric Sakurai-Hosomi allylation with BINAP and silver(I) triflate catalyst. The allylation of a variety of aromatic, alpha,beta-unsaturated and aliphatic aldehydes with allylic trimethoxysilane resulted in high yields and remarkable enantioselectivities. In addition, the asymmetric Mukaiyama-type aldol reaction is achieved by using trimethoxysilyl enol ethers in the presence of the same catalysts. High anti selectivity is obtained from E-silyl enol ether, while Z-silyl enol ether gives syn selectivity.     

Theoretical study of the Cp2Zr-catalyzed hydrosilylation of ethylene. Reaction mechanism including new sigma-bond activation

The Cp(2)Zr-catalyzed hydrosilylation of ethylene was theoretically investigated with DFT and MP2-MP4(SDQ) methods, to clarify the reaction mechanism and the characteristic features of this reaction. Although ethylene insertion into the Zr-SiH(3) bond of Cp(2)Zr(H)(SiH(3)) needs a very large activation barrier of 41.0 (42.3) kcal/mol, ethylene is easily inserted into the Zr-H bond with a very small activation barrier of 2.1 (2.8) kcal/mol, where the activation barrier and the energy of reaction calculated with the DFT(B3LYP) method are given and in parentheses are those values which have been corrected for the zero-point energy, hereafter. Not only this ethylene insertion reaction but also the coupling reaction between Cp(2)Zr(C(2)H(4)) and SiH(4) easily takes place to afford Cp(2)Zr(H)(CH(2)CH(2)SiH(3)) and Cp(2)Zr(CH(2)CH(3))(SiH(3)) with activation barriers of 0.3 (0.7) and 5.0 (5.4) kcal/mol, respectively. This coupling reaction involves a new type of Si-H sigma-bond activation which is similar to metathesis. The important interaction in the coupling reaction is the bonding overlap between the d(pi)-pi bonding orbital of Cp(2)Zr(C(2)H(4)) and the Si-H sigma orbital. The final step is neither direct C-H nor Si-C reductive elimination, because both reductive eliminations occur with a very large activation barrier and significantly large endothermicity. This is because the d orbital of Cp(2)Zr is at a high energy. On the other hand, ethylene-assisted C-H reductive elimination easily occurs with a small activation barrier, 5.0 (7.5) kcal/mol, and considerably large exothermicity, -10.6 (-7.1) kcal/mol. Also, ethylene-assisted Si-C reductive elimination and metatheses of Cp(2)Zr(H)(CH(2)CH(2)SiH(3)) and Cp(2)Zr(CH(2)CH(3))(SiH(3)) with SiH(4) take place with moderate activation barriers, 26.5 (30.7), 18.4 (20.5), and 28.3 (31.5) kcal/mol, respectively. From these results, it is clearly concluded that the most favorable catalytic cycle of the Cp(2)Zr-catalyzed hydrosilylation of ethylene consists of the coupling reaction of Cp(2)Zr(C(2)H(4)) with SiH(4) followed by the ethylene-assisted C-H reductive elimination.     

New odorless method for the Corey-Kim and Swern oxidations utilizing dodecyl methyl sulfide (Dod-S-Me)

Development of the odorless dodecyl methyl sulfide (Dod-S-Me, 1) as an alternative for dimethyl sulfide (DMS) and new odorless methods for the Corey-Kim and Swern oxidations are described. These reactions have been developed with a view toward green chemistry, utilizing Dod-S-Me (1) and common solvents instead of dichloromethane.     

Synthesis of 1,2-dihydroisoquinolines via the reaction of ortho-alkynylarylimines with bis-π-allylpalladium

The reaction of the ortho-alkynylarylimines 1 with allyltributylstannane and allyl chloride in the presence of allylpalladium chloride dimer (5 mol %) and Cu(OAc)₂ (20 mol %) in CH₃CN at 50 °C gave the 1,4-diallyl-1,2-dihydroisoquinolines 2 in good yields. Most probably, the reaction proceeds through tandem bis-allylation of the imine-alkyne functional groups with bis-π-allylpalladium.     

The synthesis of hexahydrooxoepithiopyridinedicarboximides by the reaction of thioamides with N-substituted maleimides

The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X₂ = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated.