Novel Z-selective head-to-head dimerization of terminal alkynes catalyzed by lanthanide half-metallocene complexes

Various terminal alkynes have been cleanly dimerized into the corresponding head-to-head (Z)-enynes by use of the half-metallocene lutetium alkyl complexes Me2Si(C5Me4)(NAr)Lu(CH2SiMe3)(THF) (Ar = Ph, C6H3Me2-2,6, C6H2Me3-2,4,6) as catalysts. Aromatic C-Cl, C-Br, and C-I bonds, which are known to be extremely susceptible to reductive cleavage by transition metals, survived in the present reactions. The corresponding dimeric alkynide species [Me2Si(C5Me4)(NAr)Lu(mu-CCR)]2 are thought to be the true catalysts, some of which have been isolated and structurally characterized. These alkynide species were thermally stable and soluble at the reaction temperatures (80-110 degrees C), but they precipitated upon cooling to room temperature after completion of the reaction. Therefore, this catalyst system works homogeneously but can be separated and reused, thus constituting the first example of a recyclable catalyst system for the dimerization of terminal alkynes and also the first example of (Z)-selective head-to-head dimerization of aromatic terminal alkynes.     

Synthesis,structure, and magnetic properties of dinuclear cobalt(II) complexes with a new phenol-based dinucleating ligand with four hydroxyethyl chelating arms

A new end-off type acyclic ligand with four hydroxyethyl arms, 2,6-bis[bis(2-hydroxyethyl)aminomethyl]-4-methylphenol [H(bhmp)], formed dinuclear cobalt(II) complexes [Co(2)(bhmp)(OAc)(2)]BPh(4) (1) and [Co(2)(bhmp)(OBz)(2)]BPh(4) (2). The complex 1.2.5CH(3)CN (C(50)H(62.5)BCo(2)N(4.5)O(9)) crystallizes in the monoclinic space group C2/c with dimensions a = 25.424(5) A, b = 13.376(2) A, c = 29.913(6) A, beta = 105.930(3) degrees, and V = 9781(3) A(3) and with Z = 8. X-ray diffraction analysis revealed a mu-phenoxo-bis(mu-acetato)dicobalt(II) core structure containing two octahedral cobalt(II) ions. Electronic spectra were investigated for 1 and 2 in the range 400-1800 nm, and the data were typical for the octahedral high-spin cobalt(II) complexes. Magnetic susceptibility was measured for 1 and 2 over the temperature range 4.5-300 K, and the data were analyzed well using our theoretical method. The best fitting parameters were kappa = 0.77, lambda = -116 cm(-1), Delta = 572 cm(-1), and J = -0.44 cm(-1) for complex 1 and kappa = 0.96, lambda = -93 cm(-1), Delta = 616 cm(-1), and J = -0.33 cm(-1) for complex 2.     

The acid-catalyzed rearrangement of 1-N-allylindolines

Zinc chloride-catalyzed rearrangement of 1-N-allylindoline and 1-N-(2-methylallyl)indoline proceeds readily in refluxing xylene to give 7-allylindoline and 7-(2-methylallyl)indoline in 73% and 86% yields, respectively. The reaction of 1-N-2-butenylindoline and zinc chloride give rise to the mixture of 7-(1-methylallyl)indoline, 7-(cis- and trans-1-methyl-1-propenyl)indoline, and 7-(trans-2-butenyl)indoline. On the other hand, the similar reaction of 1-N-(3-methyl-2-butenyl)indoline with zinc chloride led to the formation of a mixture of 1,2,5,6-tetrahydro-4,4-dimethyl-4H-pyrrolo[3,2,1-ij]quinoline and 7-(3-methyl-2-butenyl)indoline.     

Synthesis and complexing properties of bis-crown ethers incorporating benzo-15-crown-5 and metallocene

Bis-crown ethers in which the benzo-15-crown-5 units were linked to 1,1′-positions of metallocene (M = Fe or Ru) with amide, ester, or ? C? C? bonds were synthesized. Complexing ability of the compounds with alkali, alkali earth, and transition metal cations were measured by the solvent extraction method. The results showed that these crown ethers had high affinity toward alkali metal cations (Li⁺, Na⁺, K⁺, and Rb⁺) and heavy-metal cations (Ag⁺ and Tl⁺). The difference of complexing ability for metal cations between ferrocene and ruthenocene derivatives could not be detected significantly. The extractability of metallocene-bis-crown ethers for metal cations was more larger than that of the corresponding mono-crown ethers, and irregular increments of extractability were explained by assuming the existence of a mixture of 1:1 and 2:1 complexes.     

Elastic friction drive of surface acoustic wave motor

Importance of elastic deformation control to obtain large output force with a surface acoustic wave (SAW) motor is discussed in this paper. By adding pre-load to slider, stator and slider surfaces are deformed in a few tens nanometer. Appropriate deformation in normal direction against normal vibration displacement amplitude of SAW existed. By moderate deformation, the output force of the SAW motor was enlarged up to about 10 N and no-load speed was 0.7 m/s. To produce this performance, the transducer weight and slider size were only 4.2 g and 4 x 4 mm(2).By traveling wave propagation, surface particles of the SAW device move in elliptical motion. Due to the amplitude of the elliptical motion is 10 or 20 nm order, the contact condition of the slider is very critical. To control the contact condition, namely, the elastic deformation of the slider and stator surface in nanometer order, a lot of projections were fabricated on the slider surface. The projection diameter was 20 micro m. In static condition, the elastic deformation and stress were evaluated with the FEM analysis. From this calculation and the simulation result, it is consider that the wave crest is distorted, hence the elasticity has influence on the friction drive condition.Elastic deformation of the stator surface beneath the projection from the initial position were evaluated. In 4 x 4 mm(2) square area, the sliders had from 1089 to 23,409 projections. Depression was independent to the contact pressure. However, the output force depended on the depression although the projection density were different. From the view point of the output power of the motor, the proper depression was independent to the projection density. Around 25 nm depression, the output force and output power were maximized. This depression value was almost same as the vibration displacement amplitude of the stator transducer.     

A regiocontrolled synthesis of substituted indoles by palladium-catalyzed coupling of 2-bromonitrobenzenes and 2-bromoacetanilides

The palladium-catalyzed cross-coupling reaction of 2-bromonitrobenzenes or 2-bromoacetanilides with ethylene has been used to produce a variety of substituted indoles. The mild reaction conditions and selectivity inherent in the coupling reaction have been utilized to produce regiochemically pure 4-, 5-, 6-, and 7-substituted indoles.     

A function space model approach to the rational evaluation subgroups

Let f : U → X be a map from a connected nilpotent space U to a connected rational space X. The evaluation subgroup G _*(U, X; f), which is a generalization of the Gottlieb group of X, is investigated. The key device for the study is an explicit Sullivan model for the connected component containing f of the function space of maps from U to X, which is derived from the general theory of such a model due to Brown and Szczarba (Trans Am Math Soc 349, 4931–4951, 1997). In particular, we show that non Gottlieb elements are detected by analyzing a Sullivan model for the map f and by looking at non-triviality of higher order Whitehead products in the homotopy group of X. The Gottlieb triviality of a fibration in the sense of Lupton and Smith (The evaluation subgroup of a fibre inclusion, 2006) is also discussed from the function space model point of view. Moreover, we proceed to consideration of the evaluation subgroup of the fundamental group of a nilpotent space. In consequence, the first Gottlieb group of the total space of each S ¹-bundle over the n-dimensional torus is determined explicitly in the non-rational case.      

Global solvability for the Kirchhoff equations in exterior domains of dimension three

We consider the initial (boundary) value problem for the Kirchhoff equations in exterior domains or in the whole space of dimension three, and show that these problems admit time-global solutions, provided the norms of the initial data in the usual Sobolev spaces of appropriate order are sufficiently small. We obtain uniform estimates of the L¹(R) norms with respect to time variable at each point in the domain, of solutions of initial (boundary) value problem for the linear wave equations. We then show that the estimates above yield the unique global solvability for the Kirchhoff equations.     

Palladium-catalyzed synthesis of indoles from 2-nitrostyrenes

In the presence of palladium salts, oxidation of 2-nitrostyrenes 1 with nitrous acid alkyl esters 2 resulted in the formation of 2-nitrophenylacetaldehyde dialkyl acetals 3. Reductive cyclization of the acetals 3 with iron powder in acetic acid afforded indoles 5 in good yield.