Direct and selective arylation of tertiary silanes with rhodium catalyst

We have developed a convenient and efficient approach to the arylation of tertiary silanes under mild conditions. A variety of arylsilanes were synthesized in a one-step process with good to excellent yields in the presence of a rhodium catalyst with a base. The reaction was highly solvent dependent, and amides were the most effective of the various solvents used. This common catalyst system is highly tolerant of the various sensitive functional groups on the substrates, which might be difficult to extract by other methods. The rhodium-promoted silylation of aryl halides with electron-donating groups occurred more efficiently than the silylation of aryl halides substituted with electron-withdrawing groups. Heteroaromatic halides were also found to be readily silylated with tertiary silanes. The successful application of this reaction to the synthesis of a TAC-101 analogue, which is a trialkylsilyl-containing synthetic retinoid benzoic acid derivative with selective binding affinity for retinoic acid receptor-alpha, is also described.     

N-heterocyclic carbene-catalyzed nucleophilic aroylation of fluorobenzenes

In N-heterocyclic carbene (NHCs) catalyzed nucleophilic substitution of fluorobenzenes, fluoro groups are replaced by aroyl groups, which are derived from aromatic aldehydes. 1,3,4,5-Tetramethylimidazol-2-ylidene is found to be an efficient catalyst. The catalyst loading can be reduced to 1 mol % without a significant decrease in the product yields. Polysubstituted benzophenones are synthesized from fluorobenzenes and benzaldehydes by the NHC-catalyzed aroylation.     

Relative rotational motion between alpha-Cyclodextrin Derivatives and a stiff axle molecule

Novel [2]rotaxanes bearing alpha-cyclodextrin (alpha-CD) derivatives and a diphenylacetylene axis molecule with trinitrobenzene as a bulky stopper have been prepared to investigate the relative rotary movement of a ring relative to an axis molecule and that of an axis molecule in a ring by NMR techniques. [2]Rotaxanes 2 and 3 were composed of alpha-CD derivatives (2: 6-phenyl-amide-alpha-CD; 3: 6-stilbene-amide-alpha-CD). The protons of alpha-CDs in rotaxanes were thoroughly assigned by the two-dimensional NMR techniques (TOCSY, COSY, ROESY, HMQC, and HMBC). The protons of alpha-CD in rotaxane 1 did not show splitting, whereas the resonance peak shifts and splitting for the corresponding protons of alpha-CD derivatives in rotaxanes 2 and 3 were observed by the shielding and deshielding effects from a diphenylacetylene axis molecule. The splitting of resonance peaks was closely related to the rotary movements of alpha-CDs and an axis molecule. We supposed that alpha-CD in rotaxane 1 rotates freely around a diphenylacetylene axis molecule, and vice versa, whereas the rotary movement of alpha-CD derivatives and the axis molecules of rotaxanes 2 and 3 were restricted by the steric repulsion between the substituent group of alpha-CD and the stopper group of an axis molecule. To estimate the relative rotary movement of CDs and an axis molecule in rotaxanes, the rotational correlation time (tauc) of rotaxanes was measured by 13C NMR. The results indicate that the corresponding rotary movement of the modified alpha-CD and the axis molecules in rotaxanes 2 and 3 depends on the size of the substituent group.     

Activation of C–H and H–H bonds by dinuclear iridium complexes. Oxidative addition to highly active unsaturated 32e− diiridium species

Reactions of [(Cp¹Ir)₂(μ-dmpm)(μ-H)₂][OTf]₂ (1) with NaO^tBu in aromatic solvent at room temperature give [(Cp¹Ir)(H)(μ-dmpm)(μ-H)(Cp¹Ir)(Ar)][OTf] [Ar = Ph (3), p-Tol (4a), m-Tol (4b), 2-furyl (5a), 3-furyl (5b)] via intermolecular aromatic C–H activation. Treatment of [(Cp¹Ir)₂(μ-dppm)(μ-H)₂][OTf]₂ (2) with weak base (Et₂NH) results in intramolecular C–H activation of a phenyl group in the dppm ligand to give [(Cp¹Ir)(H){μ-PPh(C₆H₄)CH₂PPh₂}(μ-H)(Cp¹Ir)][OTf] (6). Reaction of 1 with NaO^tBu in tetrahydrofuran under H₂ (1 atm) results in activation of the H–H bond to give [{(Cp¹Ir)(H)}₂(μ-dmpm)(μ-H)][OTf] (7). Reaction of 1 with NaO^tBu in dichloromethane under carbon monoxide (1 atm) gives a carbonyl-bridged Ir^II–Ir^II complex, [(Cp¹Ir)₂(μ-dmpm)(μ-H)(μ-CO)][OTf] (8-OTf). These results strongly suggest that the active species in C–H and H–H bond activation starting with 1 and 2 would be unsaturated 32e^? diiridium species. The structures of 3, 5a, 6, 7, and 8-BPh₄ have been determined by X-ray diffraction methods.     

Light-induced hydrogen production by photosystem I–Pt nanoparticle conjugates immobilized in porous glass plate nanopores

In recent years, a number of light-induced hydrogen production systems composed of photosystem I (PSI) and hydrogen production catalysts (e.g. hydrogenases and Pt nanoparticles) have been reported. However, the utility of these systems under aerobic conditions is limited due to their poor stability in the presence of oxygen. The development of light-induced hydrogen production systems that work under aerobic conditions is, therefore, of great importance to establish artificial photosynthetic devices. Ideally, these systems should utilise water as an electron source, via water splitting by photosystem II (PSII). We report the construction of a novel light-induced hydrogen production system composed of PSI-platinum nanoparticle conjugates and cytochrome c ₆ (cyt c ₆) immobilised in nanoporous glass plates (PGP50, 50-nm pore diameter). PSI trimer (PSI_t) from Thermosynechococcus elongatus and Pt nanoparticles (PtNPs) were conjugated via electrostatic interactions (PSI_t-PtNP). PSI_t-PtNP and cyt c ₆ were spontaneously absorbed in nanopores of PGP50 without denaturation. Upon irradiation in the presence of ascorbate as a sacrificial electron donor, catalytic H₂ evolution was observed for PSI_t-PtNP immobilised in the pores of PGP50 (PSI_t-PtNP/PGP50) under both anaerobic and aerobic conditions, indicating that an effective photoinduced electron transfer system had been established. PSI_t-PtNP/PGP50 was found to exhibit improved oxygen resistivity over the homogeneous solution system consisting of PSI_t-PtNP, cyt c ₆, and ascorbate, suggesting that the PSI_t-PtNP/PGP50 system could be a potential candidate for artificial photosynthetic systems. The distribution of the components, PSI_t-PtNP and cyt c ₆, in PGP50 was characterised to discuss the efficiency of light-induced hydrogen production.     

Protein adsorption and stability of poly(ethylene oxide)-modified surfaces having hydrophobic layer between substrate and polymer

The materials covered with poly(ethylene oxide) (PEO) are of use in a wide variety of biomaterials due to blood compatibility of this polymer. The long-term sustainability of its blood compatibility strongly depends on the stability of the PEO layer against aqueous environment. An attempt was made in the present work to immobilize a PEO layer on the silicon surfaces using a silane coupling agent with the aim to improve the waterproof durability of the layer. Several kinds of PEO-modified substrates having a densely and closely packed hydrocarbon layer between substrate and PEO layer were prepared and the stability of the PEO layer against phosphate buffer saline (pH 7.4) was examined in terms of the density of hydrocarbon chains. Those substrates which have a dense hydrophobic chain layer showed a high waterproof durability and a good ability to suppress protein adsorption.     

Preparation of thin polymer films with controlled drug release

Poly(N-isopropylacrylamide) (PAAm) is a thermal responsive polymer that undergoes a structural change in aqueous solution at its lower critical solution temperature (LCST). PAAm-modified silicon substrates were prepared and the effect of PAAm density on the thermal response of the modified surface was examined in terms of changes in the water contact angle as a basis for applying the structural change of the polymer to controlled drug release. Changes with temperature in the ability to load and release of the modified layer for drug were also examined using 2-acetoxybenzoic acid (aspirin) as a model drug. The amount of PAAm was found to greatly affect the thermal response and the ability to load and release of the modified layer for aspirin.     

Synthesis and characterization of mononuclear ruthenium(III) pyridylamine complexes and mechanistic insights into their catalytic alkane functionalization with m-chloroperbenzoic acid

A series of mononuclear RuIII complexes [RuCl2(L)]+, where L is tris(2-pyridylmethyl)amine (TPA) or one of four TPA derivatives as tetradentate ligand, were prepared and characterized by spectroscopic methods, X-ray crystallography, and electrochemical measurements. The geometry of a RuIII complex having a non-threefold-symmetric TPA ligand bearing one dimethylnicotinamide moiety was determined to show that the nicotine moiety resides trans to a pyridine group, but not to the chlorido ligand. The substituents of the TPA ligands were shown to regulate the redox potential of the ruthenium center, as indicated by a linear Hammett plot in the range of 200 mV for RuIII/RuIV couples with a relatively large rho value (+0.150). These complexes act as effective catalysts for alkane functionalization in acetonitrile with m-chloroperbenzoic acid (mCPBA) as terminal oxidant at room temperature. They exhibited fairly good reactivity for oxidation of cyclohexane (C--H bond energy 94 kcal mol(-1)), and the reactivity can be altered significantly by the electronic effects of substituents on TPA ligands in terms of initial rates and turnover numbers. Catalytic oxygenation of cyclohexane by a RuIII complex with 16O-mCPBA in the presence of H2 18O gave 18O-labeled cyclohexanol with 100% inclusion of the 18O atom from the water molecule. Resonance Raman spectra under catalytic conditions without the substrate indicate formation of a RuIV==O intermediate with lower bonding energy. Kinetic isotope effects (KIEs) in the oxidation of cyclohexane suggest that hydrogen abstraction is the rate-determining step and the KIE values depend on the substituents of the TPA ligands. Thus, the reaction mechanism of catalytic cyclohexane oxygenation depends on the electronic effects of the ligands.     

An artificial molecular chaperone: poly-pseudo-rotaxane with an extensible axle

Poly-pseudo-rotaxanes CDs contains as a subset 1 (CDs; cyclodextrins, 1; poly(delta-valerolactone) having single beta-CD at the end of the polymer chain) initiate polymerization of delta-valerolactone (delta-VL) in the solid state when CDs (alpha-CD, beta-CD, and 2,6-di-O-methyl-beta-CD) are threaded onto the polymer chain. 1 without threaded CDs did not show any polymerization ability for delta-VL. An adamantane molecule (Ad) inhibited the polymerization ability of CDs contains as a subset 1 for delta-VL, indicating that beta-CD at the end of CDs contains as a subset 1 could not bind delta-VL because the beta-CD cavity was occupied by Ad. It should be noted that the insertion reaction and the polymerization took place inside the beta-CD cavity at the end of CDs contains as a subset 1 and that the formation of poly-pseudo-rotaxane is necessary for the initiation of delta-VL. The structures of beta-CD contains as a subset 1 and 1 were characterized by powder X-ray diffraction measurements and solid-state NMR spectroscopies. The polymer chain of beta-CD contains as a subset 1 was found to elongate in the solid state, whereas the polymer chain of 1 formed a random coil conformation. 1 was deactivated for the polymerization by blocking the active cavity of beta-CD with the polymer chain. CDs threaded onto 1 are immune to the initiation of delta-VL directly but have an essential role to fold the polymer chain in a proper way as an artificial chaperone.     

Development of novel hemilabile Segphos P-P=O ligands

Development of novel chiral hemilabile Segphos P-P=O ligands is described. The ligands are examined for enantioselective Pd-catalyzed allylic alkylation of cyclic allylic acetates.