Tungsten(0)- and rhenium(I)-catalyzed tandem cyclization of acetylenic dienol silyl ethers based on geminal carbo-functionalization of alkynes

Tungsten(0)- and rhenium(I)-catalyzed reactions of acetylenic dienol silyl ethers based on the concept of geminal carbo-functionalization of alkynes are reported. Treatment of 3-siloxy-1,3-diene-7-ynes with catalytic amounts of [W(CO)(6)] or [ReCl(CO)(5)] under photoirradiation conditions gives synthetically useful bicyclo[3.3.0]octane derivatives in good yields. Extremely high catalytic activity is noted for the rhenium(I) complex. The reaction has been extended to substrates containing a nitrogen atom in their tethers. In this case, two kinds of synthetically useful heterocyclic compounds-the 2-azabicyclo[3.3.0]octane derivatives 9 and the monocyclic dihydropyrroles 10, with allenyl substituents-are obtained, and selective preparation of either product can be achieved through the use of an appropriate combination of the nitrogen substituent and the type of the rhenium(I) catalyst. The 2-azabicyclo[3.3.0]octane derivatives 9 are obtained selectively by carrying out treatment of N-Ns derivatives in the presence of [ReCl(CO)(4)(PPh(3))], whereas the dihydropyrrole derivatives 10 are obtained by treatment of N-Mbs derivatives with [ReCl(CO)(5)]/AgSbF(6) . Finally, we have applied this geminal carbo-functionalization to one-carbon-elongated substrates containing N-Ts moieties in their tethers. Selective 5-exo cyclization is achieved in the presence of gold(I) or rhenium(I) catalysts, whereas 6-endo cyclization is observed on use of [W(CO)(6)].     

Guest-induced self-assembly of a macrocyclic boronic ester containing diarylethene units: enhancement of photoresponsivity

Guest-induced self-assembly of a macrocyclic boronic ester containing photochromic diarylethene units is realized and this macrocycle showed high quantum yield of photoisomerization due to favourable conformational constraint.     

Premodified Surface Method to Obtain Ultra‐Highly Dispersed Metals and their 3D Structure Control on an Oxide Single‐Crystal Surface

Precise control of the three‐dimensional (3D) structure of highly dispersed metal species such as metal complexes and clusters attached to an oxide surface has been important for the development of next‐generation high‐performance heterogeneous catalysts. However, this is not easily achieved for the following reasons. (1) Metal species are easily aggregated on an oxide surface, which makes it difficult to control their size and orientation definitely. (2) Determination of the 3D structure of the metal species on an oxide powder surface is hardly possible. To overcome these difficulties, we have developed the premodified surface method, where prior to metal deposition, the oxide surface is premodified with a functional organic molecule that can strongly coordinate to a metal atom. This method has successfully provided a single metal dispersion on an oxide single‐crystal surface with the 3D structure precisely determined by polarization‐dependent total reflection fluorescence X‐ray absorption fine structure (PTRF‐XAFS). Here we describe our recent results on ultra‐high dispersions of various metal atoms on TiO₂(110) surfaces premodified with mercapto compounds, and show the possibility of fine tuning and orientation control of the surface metal 3D structures.     

Rhodium‐Catalyzed C−H Activation Enabled by an Indium Metalloligand

Rhodium complexes with an indium metalloligand were successfully synthesized by utilizing a pyridine‐tethered cyclopentadienyl ligand as a support for an In?Rh bond. The indium metalloligand dramatically changes the electronic and redox properties of the rhodium metal, thereby enabling catalysis of sp²C?H bond activation.     

Na2O overlayers epitaxially prepared on Pd(100) and structure-sensitive CO2 adsorption

Sodium oxide overlayers prepared on Pd(100) were examined with AES, LEED and XPS. The oxides were grown by cycles of Na deposition followed by oxidation, maintaining the composition of Na₂O. The surface structure of the deposited oxide was sensitive to the annealing temperature after oxidation. The Na₂O/Pd(100) surfaces gave rise to a (3 × 3) LEED pattern when annealed at 600 K under vacuum. A model based on Na₂O(100) was proposed for the (3 × 3) overlayers, where the oxide was epitaxially aligned in a square periodicity on the substrate. Multilayered Na₂O was prepared maintaining the (3 × 3) pattern, by repeated cycles of preparation. Annealing at 700 K caused a c(4 × 6) pattern, for which a model based on Na₂O(110) was proposed. CO₂ was adsorbed on the (3 × 3) oxide of various thickness to form carbonate at 350 K, whereas the c(4 × 6) oxide was inert. The relationship of structure and reactivity is discussed in relation to the microscopic design of metal-oxide surfaces for base-catalysis.     

Recent progress in surface scientific approaches to oxide catalysis

This paper attempts to review recent work on in-situ characterizations of metals and metal oxides supported on oxide surfaces relevant to oxide catalysis. The active well-defined surfaces can provide novel information on the key issues in catalytic research such as the structure, composition and distribution of active sites, ensembles and phases, behavior of adsorbed active species, electronic property participating in catalysis, etc., which are well characterized by recent in-situ spectroscopy and also by traditional spectroscopy.     

Chiral self-dimerization of vanadium complexes on a SiO2 surface for asymmetric catalytic coupling of 2-naphthol: structure, performance, and mechanism

Vanadium monomers with chiral tridentate Schiff-base ligands were supported on SiO(2) through a chemical reaction with surface silanols, where we found a new chirality creation by the self-dimerization of the vanadyl complexes on the surface. The chiral self-dimerization and the role of surface silanols in the self-assembly were investigated by means of X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), diffuse-reflectance ultraviolet/visible (DR-UV/VIS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), electron spin resonance (ESR), and density functional theory (DFT) calculations. The surface vanadyl complexes had a distorted square-pyramidal conformation with a V=O bond. FT-IR spectra revealed that the Ph-O moiety of Schiff-base ligands was converted to Ph-OH by a surface-concerted reaction between the vanadium precursors and surface SiOH groups. The Ph-OH in an attached vanadyl complex interacted with a COO moiety of another vanadyl complex by hydrogen bonding to form a self-dimerized structure at the surface. The interatomic distance of V-V in the surface self-assembly was evaluated to be 0.40 +/- 0.05 nm by ESR after O(2) adsorption. The self-dimerized V structure on SiO(2) was modeled by DFT calculations, which demonstrated that two vanadium monomers with Ph-OH linked together by two hydrogen bonds and their V=O groups were directed opposite to each other. The surface self-dimerization of the vanadium precursors fixes the direction of the V=O bond and the plane of the Schiff-base ligand. Thus, a new chiral reaction field was created by two types of chirality: the chiral Schiff-base ligand and the chiral V center. We have also found that the chiral self-dimerized vanadyl complexes exhibit remarkable catalytic performance for the asymmetric oxidative coupling of 2-naphthol: 96% conversion, 100% selectivity to 1,1'-binaphthol (BINOL), and 90% enantiomeric excess (ee). Increasing the vanadium loading on SiO(2) caused a dramatic swell of enantioselectivity, and the maximum 90% ee was observed on the supported catalyst with the full coverage of the vanadyl complex (3.4 wt % vanadium). This value is equivalent to the maximum ee reported in homogeneous catalysis for the coupling reaction. Furthermore, the supported vanadium dimers were reusable without loss of the catalytic performance. To our knowledge, this is the first heterogeneous catalyst for the asymmetric oxidative coupling of 2-naphthol.     

A facile method for the synthesis of polycyclic indole derivatives: the generation and reaction of tungsten-containing azomethine ylides

Treatment of N-(o-alkynylphenyl)imine derivatives with W(CO)(5)(L) induces the 5-endo-mode of cyclization of the imine nitrogen onto the electrophilically activated alkyne moiety to afford a novel reactive species, a metal-containing azomethine ylide. [3 + 2] cycloaddition of this ylide species with various electron-rich alkenes proceeds smoothly to give unstable carbene complexes, which in turn undergo 1,2-hydrogen-, alkyl-, and aryl-migration to afford in good yield 6-5-5 tricyclic indole skeletons having an alkyl or an aryl substituent at the 3-position of the indole nucleus.     

Synthetic control leading to chiral compounds

A highly diastereoselective cross aldol reaction is developed using divalent tin enolates formed from stannous trifluoromethanesulfonate and carbonyl compounds. The reaction is extended to a highly enantioselective cross aldol reaction employing chiral diamines derived from (S)-proline as ligands.