Molybdenum-catalyzed reduction of molecular dinitrogen under mild reaction conditions

Quite recently we have found two nitrogen fixation systems catalyzed by molybdenum-dinitrogen complexes under mild reaction conditions; one is the transformation of molecular dinitrogen into its synthetic equivalent of ammonia and the other is that into ammonia. A molybdenum-dinitrogen complex bearing two ferrocenyl diphosphines works as a good catalyst in the transformation of molecular dinitrogen into silylamine, where up to 226 equiv are produced based on the catalyst. A dinitrogen-bridged dimolybdenum complex bearing a PNP-type pincer ligand works as a good catalyst in the direct transformation of molecular dinitrogen into ammonia, where up to 23 equiv are produced based on the catalyst. We believe that both systems provide a new aspect in the development of novel nitrogen fixation.     

Intramolecular oxycyanation of alkenes by cooperative Pd/BPh3 catalysis

The cooperative catalysis by palladium and triphenylborane effects the intramolecular oxycyanation of alkenes through the cleavage of O-CN bonds and the subsequent insertion of double bonds. The use of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) as a ligand for palladium is essential for allowing the transformation to proceed with high chemo- and regioselectivity. Variously substituted dihydrobenzofurans with both a tetra-substituted carbon and cyano functionality are accessed by the newly developed methodology.     

Photoinduced electron transfer and excitation energy transfer in directly linked zinc porphyrin/zinc phthalocyanine composite

Photoinduced electron transfer (ET) and excitation energy transfer (ENT) reactions in monomer and slipped-cofacial dimer systems of a directly linked Zn porphyrin (Por)-Zn phthalocyanine (Pc) heterodyad, ZnPc-ZnPor, were investigated by means of the picosecond and femtosecond transient absorption spectroscopies. In the dimer dyad system of two heterodyads connected through the coordination bond between two imidazolyl-substituted ZnPor bearing ZnPc, ZnPc-ZnPor(D), the rapid ENT from the ZnPor to ZnPc in the subpicosecond time region was followed by photoinduced charge separation (CS) and charge recombination (CR) with time constants of 47 and 510 ps, respectively. On the other hand in the monomer dyad system, no clear charge-separated state was observed although the CS with a time constant of 200 ps and CR with < or =70 ps were estimated. These results indicated that the dimer slipped-cofacial arrangement of pair porphyrins is advantageous for the effective production of the CS state. This advantage was discussed from the viewpoint of a decrease in the reorganization energy of the dimer relative to that of the monomer system. In addition, the electrochemical measurements indicated that the strong interaction between ZnPc and ZnPor moieties also contributed to the fast CS process despite the marginal driving force for the CS process. The dimer dyad of ZnPc-ZnPor provides full advantages in efficiencies of the light harvesting and the CS state production.     

Ruthenium-catalyzed propargylic substitution reaction of propargylic alcohols with thiols: a general synthetic route to propargylic sulfides

A novel cationic methanethiolate-bridged diruthenium complex [Cp*RuCl(mu2-SMe)2RuCp*(OH2)]OTf (1e) has been disclosed to promote the catalytic propargylic substitution reaction of propargylic alcohols bearing not only terminal alkyne group but also internal alkyne group with thiols. It is noteworthy that neutral thiolate-bridged diruthenium complexes (1a-1c), which were known to promote the propargylic substitution reactions of propargylic alcohols bearing a terminal alkyne group with various heteroatom- and carbon-centered nucleophiles, did not work at all. The catalytic reaction described here provides a general and environmentally friendly preparative method for propargylic sulfides, which are quite useful intermediates in organic synthesis, directly from the corresponding propargylic alcohols and thiols.     

Enantioselective carbon–carbon bond forming reactions using fluorous chiral catalysts

Fluorous chiral BINOLs and BINAP were prepared and used as the ligands for an asymmetric addition of Et₂Zn to aromatic aldehydes and an asymmetric Heck reaction, respectively. The enantioselectivities were similar in homogeneous system to those of the original non-fluorous reactions. Consecutive reactions were examined by utilizing fluorous–organic biphase and fluorous solid phase extraction techniques. Enantioselectivities in consecutive reactions were close to that attained in the non-fluorous system. The solid phase extraction method also enabled us to perform a simultaneous screening procedure.     

Irreversible helix rearrangement from Cis‐transoid to Cis‐cisoid in poly(p‐n‐hexyloxyphenylacetylene) induced by heat‐treatment in solid phase

Polymerization of p‐n‐hexyloxyphenylacetylene (pHPA) by using a [Rh(norbornadine)Cl]₂‐triethylamine catalyst was carried out at room temperature to afford stereoregular helical poly(p‐n‐hexyloxyphenylacetylene)s (PpHPAs). When ethanol and n‐hexane were used as polymerization solvents, a bright yellow PpHPAs, poly( Y ) with M_n = 8.5 × 10⁴ and its purple red polymer, poly( R ) with M_n = 5.3 × 10⁴ were obtained in 95% yields and 84% yields, respectively. Diffuse reflective UV–vis spectra of poly( Y ) and poly( R ) in solid phase showed different broad absorption peaks at 445 and 575 nm, respectively. X‐Ray diffraction patterns of poly( Y ) and poly( R ) showed typical columnar structures assignable to cis‐transoid and cis‐cisoid structures, respectively, which were also supported by molecule mechanics calculation. Poly( Y ) was irreversibly transformed to a reddish‐black polymer, poly( Y‐B ), which columnar diameter was nearly the same as that of poly( R ). Further, poly( Y ) showed an exothermic peak in the differential scanning calorimetry trace at 80 °C for 1 h in N₂ gas. Thus, these findings suggest a thermally irreversible rearrangement from an unstable cis‐transoid form, poly( Y ) with a stretched cis‐transoid helix to a stable cis‐cisoid form, poly( R ), with a contracted cis‐cisoid helix in the solid phase to give poly( Y → B ) with the cis‐cisoid form. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Imaging of enzyme activity by scanning electrochemical microscope equipped with a feedback control for substrate-probe distance

The enzymatic activity of diaphorase (Dp) immobilized on a solid substrate was characterized using a scanning electrochemical microscope (SECM) with shear force feedback to control the substrate-probe distance. The shear force between the substrate and the probe was monitored with a tuning fork-type quartz crystal and used as the feedback control to set the microelectrode probe close to the substrate surface. The sensitivity and the contrast of the SECM image were improved in the constant distance mode (distance, 50 nm) with the shear force feedback compared to the image in the constant height mode without the feedback. By using this system, the SECM and topographic images of the immobilized diaphorase were simultaneously measured. The microelectrode tip used in this study was ground aslant like a syringe needle in order to obtain the shaper topographic images. This shape was also effective for avoiding the interference during the diffusion of the enzyme substrates.     

Organic hybrid of chlorinated polyethylene and hindered phenol. II. Influence of the chemical structure of small molecules on viscoelastic properties

The viscoelastic properties and stabilities of those properties of organic hybrids consisting of chlorinated polyethylene (CPE) and tetrakis[methylene‐3‐(3‐5‐di‐tert‐butyl‐4‐hydroxy phenyl)propionyloxy]methane (AO‐60) and triethylene glycol bis[3‐(3‐tert‐butyl‐4‐hydroxy‐5‐methyl phenyl)propionyloxy] (AO‐70) were investigated. The CPE/AO‐70 hybrids show only one transition, whereas for the CPE/AO‐60 hybrids, one novel relaxation appears above the glass‐transition temperature of CPE. This relaxation on the higher temperature side in the mechanical spectrum for CPE/AO‐60 is associated with the appearance of the AO‐60‐rich phase. Furthermore, the stabilities of the viscoelastic properties and microstructures of the organic hybrids consisting of CPE and multifunctional hindered phenols are dominated by the strength of the intermolecular interaction between CPE and phenols and the conformations of the middle skeletal parts of hindered phenols. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1496–1503, 2000     

Efficient [3,3]-sigmatropic rearrangement accelerated by a trifluoroacetyl group: synthesis of benzofurans under mild conditions

The [3,3]-sigmatropic rearrangement took place smoothly during the course of trifluoroacetylation of O-phenyloxime at below room temperature to give the dihydrobenzofuran or benzofuran as a result of concomitant cyclization.