2 alpha-(3-hydroxypropyl)- and 2 alpha-(3-hydroxypropoxy)-1 alpha,25-dihydroxyvitamin D3 accessible to vitamin D receptor mutant related to hereditary vitamin D-resistant rickets

Hereditary vitamin D-resistant rickets (HVDRR) is a genetic disorder caused by mutations in the vitamin D receptor, which lead to resistance to 1alpha,25-dihydroxyvitamin D(3) [1alpha,25(OH)(2)D(3)]. We found that the A ring-modified analogues, 2alpha-(3-hydroxypropyl)- and 2alpha-(3-hydroxypropoxy)-1alpha,25(OH)(2)D(3), (O1C3 and O2C3) can bind better than the natural hormone to the mutant VDR (R274A), which similar to the HVDRR mutant, R274L, had lost the hydrogen bond to the 1alpha-hydroxyl group of 1alpha,25(OH)(2)D(3).     

Structures and stabilities of 3d-transition metal-benzene organometallic clusters

In the gas phase, we have successfully synthesized organometallic clusters, M_n(benzene)_m (M=3d transition metal atoms), by using a laser vaporization method. The measurements of mass spectra and ionization energies (E_i) have revealed that the organometallic clusters can take two types of structures; layered sandwich structures (m = n + 1) and metal clusters saturatedly covered with benzenes. For early transition metals of Sc, Ti, and V, only the multiple decker sandwich structure clusters were preferentially produced, in which benzene and metal atoms are alternately piled up. For late transition metals of Co and Ni, the metal clusters saturatedly surrounded by benzenes were also produced as well as the sandwich clusters. Furthermore, the E_is of M₁(benzene)₂ (M = Sc-Ni) were systematically measured and their electronic properties will be discussed.     

The reaction of isocyanide—mercuric chloride complexes with amines. Preparation of guanidines

Isocyanide—mercuric chloride complexes react readily with an excess of primary and secondary amines to give guanidines and metallic mercury in high yields through a redox decomposition reaction. In the presence of triethylamine, isocyanide—mercuric chloride complexes react with an equimolar amount of a primary amine to give a carbodiimide and metallic mercury. An intermediate organomercuric compound was isolated in the reaction of the isocyanide—mercuric chloride complex with pyrrolidone.     

Anion binding to a ferric porphyrin complexed with per-O-methylated beta-cyclodextrin in aqueous solution

5,10,15,20-Tetrakis(4-sulfonatophenyl)porphinato iron(III) (Fe(III)TPPS) forms a very stable 1:2 complex with heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMe-beta-CD), whose iron(III) center is located at a hydrophobic cleft formed by two face-to-face TMe-beta-CD molecules. Various inorganic anions (X(-)) such as F(-), Cl(-), Br(-), I(-), N(3)(-), and SCN(-) coordinate to Fe(III)TPPS(TMe-beta-CD)(2) to form five-coordinate high-spin Fe(III)TPPS(X)(TMe-beta-CD)(2), while no coordination occurs with ClO(4)(-), H(2)PO(4)(-), NO(3)(-), and HSO(4)(-). Except for F(-), none of the anions investigated coordinate to Fe(III)TPPS in the absence of TMe-beta-CD due to extensive hydration to the anions as well as to Fe(III)TPPS. The present system shows a high selectivity toward the N(3)(-) anion. The thermodynamics suggests that Lewis basicity, hydrophilicity, and shape of an X(-) anion are the main factors to determine the stability of the Fe(III)TPPS(X)(TMe-beta-CD)(2) complex.     

A highly cis-selective synthesis of 2-ethynylaziridines by intramolecular amination of chiral bromoallenes: improvement of stereoselectivity based on the computational investigation

The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by B3LYP density functional calculations together with the 6-31+G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner.     

Pyrolysis reaction of carpronium chloride and its structurally related compounds. 2—a mass spectrometric study of the lactonization mechanism

The mechanism of the pyrolysis reaction of carpronium chloride [(CH₃)₃N⁺? (CH₂)₃? COOCH₃CI^?] leading to γ-butyrolactone and tetramethylammonium chloride was investigated by means of thermal analysis, pyrolysis gas chromatography mass spectrometry and field desorption mass spectrometry, using deuterium labelling. The results indicated that carpronium chloride pyrolysed to yield equimolar amounts of γ-butyrolactone and tetramethylammonium chloride, methyl transfer occurred between N and O during the pyrolysis process. The mechanism is discussed on the basis of the experimental results, and with the aid of the theoretical results calculated by the CNDO/2 method. The mechanism presented is as follows. γ-Butyrolactone is formed by the intramolecular migration of the π-orbital of C?O to the carbon adjacent to [(CH₃)₃N]⁺ via a 5-membered ring transition state, accompanied by a bimolecular reaction between [(CH₃)₃N]⁺ and the CH₃ of O? CH₃, resulting in the formation of tetramethylammonium chloride in an amount equimolar with γ-butyrolactone.     

KINETICS AND MECHANISM OF PHOTOCYCLOADDITION OF DEOXYURIDINES TO 2,3-DIMETHYL-2-BUTENE

The mechanism of photocycloaddition of 2′-deoxyuridine (1a) and thymidine (1b) to 2,3-dimethyl-2-butene (Bu) in acetonitrile by UV irradiation has been studied. The reciprocal quantum yield for the cycloaddition increased linearly with reciprocal concentrations of Bu in acetonitrile to give limiting quantum yields at infinite concentration of Bu as 0.030 and 0.0096 for 1a and 1b , respectively. This shows that the cycloaddition proceeds in a two-step mechanism between the triplet state of 1 and Bu through biradical intermediates. Addition of cis-1,3-pentadiene quenched the reaction obeying the Stern–Volmer equation. The above quenching experiments and laser transient spectroscopy revealed that the triplet state of 1a reacts with Bu with much larger rate constant (1.3–1.6 × 10⁹ M^?1 s^?1) than that of 1b (4–5 × 10⁷ M^?1 s^?1) reflecting larger steric hindrance exerted in the reaction of 1b than that of 1a .     

Design and synthesis of spiro bis(1,2,3-triazolium) salts as chiral ionic liquids

Room temperature chiral spiro ionic liquids 1 and 2 based on 1,2,3-triazolium salts, were synthesized via an intramolecular double Huisgen reaction. The preparation of the enantiomerically pure spiro triazolium salts was achieved by resolution by HPLC using a chiral stationary phase column and subsequent N-dialkylations of spiro triazoles 6 and 10.