Resonance Raman scattering with a forbidden but vibronically allowed electronic transition: Excitation profiles of combinations and overtones of copper tetraphenylporphyrin in the Q-band resonance

Resonance Raman scattering with the Q band of CuTPP shows a peculiar intensity pattern; bands due to combinations and overtones are strong, whereas the corresponding fundamentals are very weak. By a quantitative analysis of excitation profiles, this phenomenon has been fully accounted for on the basis of the vibronic theory of Raman intensities. Vibronic coupling parameters between the Q and B states of CuTPP have been obtained.     

Ruthenium-catalyzed carbonylative cycloaddition of alpha-keto lactones with alkenes or alkynes: the participation of an ester-carbonyl group in cycloaddition reactions as the two-atom assembling unit

The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction.     

Second-derivative spectrophotometric study on the interactions of chlorpromazine and triflupromazine with bovine serum albumin

The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures.     

Ruthenium-catalyzed reaction of alpha,beta-unsaturated imines with carbon monoxide and alkenes leading to beta,gamma-unsaturated gamma-butyrolactams: involvement of direct carbonylation at olefinic C[bond]H Bonds as a key step

The reaction of alpha,beta-unsaturated imines with CO and alkenes in the presence of Ru(3)(CO)(12) as a catalyst results in a three-component coupling reaction that gives alpha,alpha-disubstituted beta,gamma-unsaturated gamma-butyrolactams. The reaction proceeds via a two-step sequence involving the initial formation of ketone derivatives by catalytic carbonylation at the beta-olefinic C-H bonds of alpha,beta-unsaturated imines, followed by the (uncatalyzed) intramolecular nucleophilic attack of the imine nitrogen on the ketonic carbon to generate a tetrahedral intermediate, which then undergoes a 1,2-ethyl migration. The reaction of a cyclic unsaturated imine, derived from the reaction of (1R)-(-)-myrtenal with tert-butylamine, gives a beta-aminocyclopentene derivative, which is formed by an aldol-type condensation of the initially formed ketone, indicating the initial formation of ethyl ketone.     

Stochastic phase lockings in a relaxation oscillator forced by a periodic input with additive noise: A first-passage-time approach

Noise effects on phase lockings in a system consisting of a piecewise-linear van der Pol relaxation oscillator driven by a periodic input are studied. The problem of finding the period of the oscillator is reduced to the first-passage-time problem of the Ornstein-Uhlenbeck process with time-varying boundary. The probability density functions of the first-passage time are used to define the operator which governs a transition of an input phase density after one cycle of the oscillator. Phase lockings in a stochastic sense are investigated on the basis of the density evolution by the operator.     

Direct catalytic asymmetric Michael reaction of hydroxyketones: asymmetric Zn catalysis with a Et2Zn/linked-BINOL complex

Full details of our direct Michael addition of unmodified ketones using new asymmetric zinc catalysis are described. Et(2)Zn/(S,S)-linked-BINOL complexes were successfully applied to direct 1,4-addition reactions of hydroxyketones. The first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was effective for 1,4-addition of 2-hydroxy-2'-methoxyacetophenone (3). Using 1 mol % of (S,S)-linked-BINOL 1 and 2 mol % of Et(2)Zn, we found that a 1,4-addition reaction of beta-unsubstituted enone proceeded smoothly at 4 degrees C to afford products in high yield (up to 90%) and enantiomeric excess (up to 95%). In the case of beta-substituted enones, however, the first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was not at all effective. The second generation Et(2)Zn/(S,S)-linked-BINOL 1 = 4/1 with MS 3A system was developed and was effective for various beta-substituted enones to afford products in good dr, yield (up to 99%), and high enantiomeric excess (up to 99% ee). With the Et(2)Zn/1 = 4/1 systems, catalyst loading for beta-unsubstituted enone was reduced to as little as 0.01 mol % (substrate/chiral ligand = 10 000). The new system was also effective for 1,4-addition reactions of 2-hydroxy-2'-methoxypropiophenone (9) to afford chiral tert-alcohol in high enantiomeric excess (up to 96% ee). Mechanistic investigations as well as transformations of the Michael adducts into synthetically versatile intermediates are also described.     

Isolation, characterization, and theoretical study of La2@C78

A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5).     

Reaction of carbon monoxide with N-lithioketimines derived by the addition of alkyllithium to ortho-substituted benzonitriles. Diverse courses of cyclization via carbonyl anions

N-Lithioketimines, generated in situ from 2-substituted benzonitriles and t-BuLi, reacted with carbon monoxide to afford five-, six- or seven-membered cyclic products, involving participation by the ortho substituents. The reactions represent new selective transformations of carbonyllithium intermediate which previously were observed to lead to complicated reactions.