用新分离的巨大芽孢杆菌对映选择性水解缩水甘油苯基醚

Microbial epoxide hydrolases from bacterial and fungal sources?1? are hi ghly versatile catalysts for the asymmetric hydrolysis of chiral epoxides which are extensively employed as useful building blocks for the synthesis of various biologically active products in the pharmaceutical and agrochemical industries. Microorganism means allows an unlimited supply of these enzymes for preparative -scale applications. Phenyl glycidyl ether (PGE), an aryl epoxide, is a potenti ally useful compound in the synthesis of chiral amino alcohols and bioactive com pounds such as ?blockers. No suitable biocatalyst with sufficiently high enan tioselectivity (E?20) for the kinetic resolution of this compound was previ ously found among bacteria and fungi. This prompted us to screen epoxide hydrola se-producing microorganisms with higher enantioselectivity toward phenyl glycid yl ether from soil samples.     

核酸碱基与甘氨酸二肽间氢键作用的最佳位点

优化得到了碱基腺嘌呤、胸腺嘧啶、尿嘧啶、鸟嘌呤及胞嘧啶与甘氨酸二肽分子形成的28个氢键复合物的稳定结构并计算了结合能, 探讨了五种碱基与甘氨酸二肽分子间氢键作用的最佳位点. 本文研究发现: 每种碱基均可以通过不同位点与二肽分子形成氢键复合物, 腺嘌呤、胸腺嘧啶、尿嘧啶、鸟嘌呤及胞嘧啶分别最倾向使用A3、T1、U1、G3及C1位点与甘氨酸二肽分子形成氢键复合物; 碱基分子某位点的质子化反应焓变越负所形成的氢键复合物越稳定, 去质子化反应焓变越小所形成的氢键复合物越稳定; 由氢键复合物的结合能计算得到的稳定性次序与由碱基分子质子化和去质子化反应焓变推得的稳定性次序一致.     

查尔酮参与的不对称Michael加成反应研究进展

综述了近十年来,金鸡纳碱、硫脲、手性离子液体、季铵盐、脯氨酸和葡萄糖类衍生物等有机小分子在催化查尔酮的不对称Michael加成反应中的应用.有机小分子催化的机理大部分都是通过氢键、离子键等与底物相互作用而使其有较好的对映选择性.     

密度泛函理论研究分子筛相邻双酸性位对乙烯质子化反应的影响

采用密度泛函理论B3LYP/6-31G(d,p)方法,研究了HZSM-5分子筛上不同酸性位以及相邻双酸性位对乙烯质子化反应的影响,考察了乙烯吸附、质子化反应过渡态和表面乙氧中间体的几何结构、原子电荷和相关能量.结果表明,存在紧邻酸性位的分子筛酸性明显减弱,乙烯分子的吸附能降低,但质子转移过渡态的活化能仅略有降低;次邻酸...     

Asymmetric Epoxidation of Olefins with Sodium Percarbonate Catalyzed by Bis-amino-bis-pyridine Manganese Complexes

Asymmetric epoxidation of a series of olefinic substrates with sodium percarbonate oxidant in the presence of homogeneous catalysts based on Mn complexes with bis-amino-bis-pyridine ligands is reported. Sodium percarbonate is a readily available and environmentally benign oxidant that is studied in these reactions for the first time. The epoxidation proceeded with good to high yields (up to 100%) and high enantioselectivities (up to 99% ee) using as low as 0.2 mol. % catalyst loadings. The epoxidation protocol is suitable for various types of substrates, including unfunctionalized alkenes, α,β-unsaturated ketones, esters (cis- and trans-), and amides (cis- and trans-). The reaction mechanism is discussed.     

Design and Synthesis of C-1 Methoxycarbonyl Derivative of Narciclasine and Its Biological Activity

A 15-step chemoenzymatic total synthesis of C-1 methoxycarbonyl narciclasine (10) was accomplished. The synthesis began with the toluene dioxygenase-mediated dihydroxylation of ortho-dibromobenzene to provide the corresponding cis-dihydrodiol (12) as a single enantiomer. Further key steps included a nitroso Diels–Alder reaction and an intramolecular Heck cyclization. The C-1 homolog 10 was tested and evaluated for antiproliferative activity against natural narciclasine (1) as the positive control. Experimental and spectral data are reported for all novel compounds.     

二溴对甲基偶氮羧质子化及其离解

用萃取法对二溴对甲基偶氮羧进行了纯化,并用分光光度法研究了二溴对甲基偶氮羧的质子化和五级离解作用,测定了其质子化常数和逐级离解常数,获得满意的效果。     

μ-Acyl Os3 clusters containing metallocenyl substituents and products of their protonation

Previously unknown μ-acyl osmium clusters containing simultaneously permethyl-metallocenyl and Os₃ cluster fragments were synthesized. The IR, UV, NMR (¹H and¹³C), and FAB-MS spectra were examined. Protonation of the clusters proceeds at the metal atom of the metallocenyl fragment. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 180–183, January, 1999.     

Giant RS spectroscopy and structural-conformational transformations of thiamine adsorbed on the surface of a silver electrode

An investigation of giant RS spectra of a thiamine (vitamin B₁) molecule adsorbed on the surface of an anodized silver electrode from weak-concentration aqueous solutions is made. The dependences of the spectral bands sensitive to the ionic state of the adsorbed molecule on the pH and the electrode potential are discussed. It is shown that the rate constant of thiamine protonation in the adsorbed layer depends on the electrode potential and is substantially lower than the corresponding value for the solution. In conformity with the important role of short-range mechanisms of enhancement of electrochemical GRS in the excitation wavelength range investigated, models of the structural-conformational states of the molecule in the adsorbed state are constructed and a conclusion is drawn about the possibility of monitoring the acid-base equilibrium of these states for a molecular layer of thiamine under the conditions of an electrochemical cell. To whom correspondence should be addressed. Ya. Kupala Grodno State University, 22, Ozheshko Str., Grodno, 230023, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 5, pp. 622–626, September–October, 1999.     

A new class of chiral pyrrolidine ligands for homogeneous catalytic enantioselective cyclopropanation of styrene

A new class of chiral pyrrolidine ligands have been successfully synthesized and their chiral induction abilities have been examined in the homogeneous catalytic enantioselective cyclo-propanation of styrene. 15-30% enantiomeric excess ( ee) has been achieved.