Synthesis of new chiral sulfinyldiacetic acid derivatives and attempt at chemoselective asymmetric Pummerer reaction

(R(S))-1 (85% ee) was prepared by utilizing a porcin pancreatic lipase-promoted hydrolysis of sulfinyldiacetic acid dimethyl ester (8) which was derived from thiodiacetic acid (7). (R(S))-1 (99% ee) and (S(S))-1 (99% ee) were readily obtained by methanolysis of (R(S),S)-12 and (S(S),S)-12 with MeONa in MeOH. (R(S),S)-12 and (S(S),S)-12 were furnished by chromatographic separation of the diastereomeric mixture, obtained by oxidation of thiodiacetic mono-carboxylic acid (11) with 30% H2O2 followed by dehydrative condensation of the resultant sulfinyldiacetic mono-carboxylic acid with 4(S)-isopropyl-1,3-thiazolidine-2-thione. (R(S))-1 (99% ee) was successively treated with (TMS)2NLi, Ac2O, and TMSOTf to give a major chiral-3 product in 75% ee and in a highly chemoselective manner (chiral-3:chiral-2=93:7).     

Intramolecular charge-transfer state formation of 4-(N,N-dimethylamino)benzonitrile in acetonitrile solution: RISM-SCF study

Intramolecular charge-transfer (ICT) state formation of 4-(N,N-dimethylamino)benzonitrile in acetonitrile solution is studied by the reference interaction site model self-consistent field (RISM-SCF) method. Geometry optimizations are performed for each electronic state in solution with the complete-active-space SCF wave functions. Dynamic electron correlation effects are taken into account by using the multiconfigurational quasidegenerate perturbation theory. Two-dimensional free energy surfaces are constructed as the function of the twisting and wagging angles of the dimethylamino group for the ground and locally excited (LE) states. The calculated absorption and fluorescence energies are in good agreement with experiments. The validity of the twisted ICT (TICT) model is confirmed in explaining the dual fluorescence, and the possibility of the planar ICT model is ruled out. To examine the mechanism of the TICT state formation, a "crossing" seam between the LE and charge-transfer (CT) state surfaces is determined. The inversion of two electronic states occurs at a relatively small twisting angle. The effect of solvent reorganization is also examined. It is concluded that the intramolecular twisting coordinate is more important than the solvent fluctuation for the TICT state formation, because the energy difference between the two states is minimally dependent on the solvent configuration.     

Mycapolyols A-F, new cytotoxic metabolites of mixed biogenesis from the marine sponge Mycale izuensis

[structure: see text]. Mycapolyols A-F (1-6), six new unusual PKS/NRPS metabolites, were isolated from the marine sponge Mycale izuensis. The gross structures were elucidated by analysis of spectroscopic data, while the stereochemistry was established using chemical method and the universal NMR database.     

Sequential flow-injection spectrophotometric determination of iron(II) and iron(III) by copper(II)-catalyzed reaction with Tiron

A flow injection method for the sequential determination of iron(II) and iron(III) was developed. It is based on the differential reaction kinetics of iron(II) and iron(III) with Tiron in a double-injection FI system. The proposed method employs the accelerating action of copper(II) for the oxidation of iron(II) in the presence of Tiron. A linear calibration graph is obtained for iron (II) and iron(III) in the concentration range 1.8 × 10^–5– 1.8 × 10^–4 mol/L; the throughput of samples is 30 injections/h. Received: 22 October 1996 / Revised: 4 December 1996 / Accepted: 10 December 1996     

Preparation of soluble ternary heteroazo dye complexes for the spectrophotometric determination of trace uranium(VI)

The complexing ability of typical pyridylazo, quinolylazo and thiazolylazo dyes with uranium(VI) in aqueous ethanol media are investigated in the presence and absence of aromatic carboxylic acid. Uranium(VI) forms solubilized ternary complexes with PAN, PAR, TAM, 5-Br-PADAP, 3,5-diBr-PADAP and QADAP in 48% ethanol solution containing sufficient amounts of sulfosalicylic acid and triethanolamine buffer (pH 7.8). Aromatic carboxylic acids contribute to expel the coordinated water molecules from the uranium (VI) moiety and their chelating effects have been explained by ternary complex formation. An increase in molar absorptivity and no shift in the wavelength of maximum absorbance are observed for all uranium(VI) complexes investigated. The 11 stoichiometry of uranuim(VI) and heteroazo dye in the binary complex does not change through ternary complex formation. The molar absorptivity of the uranium(VI)-3,5-diBr-PADAP-sulfosalicylic acid ternary complex at 595 nm is 8.4×10⁴l mol^–1 cm^–1 and Beer's law is valid up to 2.5gmg ml^–1 of uranium(VI). The interferences due to coexisting metal ions can be effectively masked by addition of CyDTA or Ca-CyDTA.     

Theoretical study on electronic and spin structures of [Fe2S2](2+,+) cluster: reference interaction site model self-consistent field (RISM-SCF) and multireference second-order Møller-Plesset perturbation theory (MRMP) approach

Electronic structures of [Fe(2)S(2)(SCH(3))(4)](2-,3-) in DMSO solution are calculated using reference interaction site model complete active space self-consistent field (RISM-CASSCF)/multireference second-order M?ller-Plesset perturbation theory (MRMP) method. For the reduced state, we obtain both the low-spin Fe(3+)Fe(2+) localized and high-spin Fe(2.5+)Fe(2.5+) delocalized forms, which are very close in energy. The spin interaction constants obtained from the energies of states with various spin multiplicities are in good agreement with the available experimental estimates both for the oxidized and for the reduced states. The dynamic electron correlation effect is found to be important in estimating the spin interaction between the Fe ions. The redox potentials are calculated to be 2.87 and 2.78 eV for the localized and delocalized reduced states, respectively, which are close to the experimental values. We devise a simple model for calculating the free energy curves of the reduction process based on the RISM-SCF theory. The activation barrier height is calculated to be 7.4 kcal/mol at the equilibrium geometry of oxidized state, indicating that the reduction reaction will occur efficiently in DMSO solvent. The effect of solvent fluctuation on the free energy profiles is discussed on the basis of the present calculations.     

Potential energy surfaces and dynamics of Ni2+ ion aqueous solution: molecular dynamics simulation of the electronic absorption spectrum

We develop a model effective Hamiltonian for describing the electronic structures of first-row transition metals in aqueous solutions using a quasidegenerate perturbation theory. All the states consisting of 3d(n) electronic configurations are determined by diagonalizing a small effective Hamiltonian matrix, where various intermolecular interaction terms such as the electrostatic, polarization, exchange, charge transfer, and three-body interactions are effectively incorporated. This model Hamiltonian is applied to constructing the ground and triplet excited states potential energy functions of Ni(2+) in aqueous solution, based on the ab initio multiconfiguration quasidegenerate perturbation theory calculations. We perform molecular dynamics simulation calculations for the ground state of Ni(2+) aqueous solution to calculate the electronic absorption spectral shape as well as the ground state properties. Agreement between the simulation and experimental spectra is satisfactory, indicating that the present model can well describe the Ni(2+) excited state potential surfaces in aqueous solution.     

Synthesis, structures, and solution behavior of di- and trinuclear titanium(IV)--cyclophosphato complexes

The reaction of the cyclotetraphosphate ion (P(4)O(12)(4)(-)) with [CpTiCl(3)] (Cp = eta(5)-C(5)Me(5)) gives [(CpTi)(2)(P(4)O(12))(2)](2)(-) where the P(4)O(12) ligands adopt a saddle conformation, while that with [(CpTiCl)(3)(mu-O)(3)] leads to [(CpTi)(3)(mu-O)(3)(P(4)O(12))](-) containing a crown form P(4)O(12) ligand; both products feature their unique cage structures. On the other hand, the reactions of the cyclotriphosphate ion (P(3)O(9)(3)(-)) with [(CpTiCl(2))(2)(mu-O)] and [(CpTiCl)(3)(mu-O)(3)] afford [(CpTi)(2)(mu-O)(P(3)O(9))(2)](2)(-) and [(CpTi)(3)(mu-O)(3)Cl(P(3)O(9))](-), respectively, and in both cases the P(3)O(9) ligands bridge two titanium centers with an eta(2):eta(1) mode.     

Multi-functionalized chiral crown ethers as enzyme models for the synthesis of peptides. Multiple chiral recognition in the enzyme model

A novel approach to the enzyme model for the synthesis of peptides has been established by using multi-functionalized chiral crown ethers as hosts. The new strategy consists of three key steps as follows. (1) Guest assembly: the host having one free thiol and one thioester withN-protected-amino acid or peptide proceeds via rapid intra-complex thiolysis of-amino acid ester salts to form the dithioester, and assembles two guests. (2) Amide formation: the intramolecular aminolysis occurs between the bound guests to form the amide bond. (3) Peptide chain elongation: as the thiol reactive group is regenerated, the above two reactions are repeated to elongate the peptide chain. In the present paper, we describe the multiple chiral recognition that could be achieved by the chiral crown ether in both the intra-complex thiolysis and the intramolecular aminolysis. For explanation of the chiral recognition, we propose a likely structure for the intermediate of the aminolysis.     

Highly efficient chemical fixations of carbon dioxide and carbon disulfide by cycloaddition to aziridine under atmospheric pressure

Cycloaddition of aziridine with carbon dioxide was successfully catalyzed by alkali metal halide or tetraalkylammonium halide to give the corresponding 5-membered cyclic urethane, 1,3-oxazolidin-2-one, selectively. The reaction can be performed at ambient temperature under atmospheric pressure. Analoguous reaction of aziridine with carbon disulfide also successfully gave the corresponding 5-membered cyclic dithiourethane, 1,3-thioxazolidine-2-thione.