环状烯酮与环状1-氮杂二烯的非对映及对映选择性[4+2]环加成反应

有机胺能催化环状烯酮化合物在多个位点发生不对称合成反应. 最近,我们发展了手性伯胺催化β-取代2-环戊烯酮与从糖精衍生的1-氮杂二烯的α’,γ-区域选择性的[5+3]形式环加成反应. 这里我们将报道采用β-取代2-环己烯酮或β-未取代2-环戊烯酮时,在手性伯胺催化下却与相同1-氮杂二烯发生完全不同的α’,β-区域选择性的不对称[4+2]环加成反应,生成高度官能团化的手性[2.2.2]或[2.2.1]桥环骨架结构. 重要的是利用不同类型的手性伯胺催化剂能够实现非对映选择性的反转,分别制备高立体选择性的endo-或exo-环加成产物.     

毛细管电色谱-电喷雾-飞行时间/质谱联用分离分析混合氨基酸对映体

建立了一种简单高效的毛细管电色谱-电喷雾-飞行时间/质谱(CEC-ESI-TOF/MS)联用技术分离混合氨基酸对映体的方法。 以D,L-精氨酸、D,L-缬氨酸和D,L-谷氨酸为研究对象,通过优化CEC分离条件和MS检测条件,3种混合氨基酸对映体的6个组分在15 min内实现了分离,分离度分别为3.03、1.59和1.37。 该方法为混合对映体的分离分析提供了参考方法和基础数据。     

D-扁桃酸脱氢酶和L-亮氨酸脱氢酶级联催化的L-苯甘氨酸对映选择性生物合成

L-苯甘氨酸是重要的手性非天然α-氨基酸,可广泛用于合成多种食品添加剂及药物中间体,探索其绿色合成工艺具有重要的意义。 本研究将新型高活性的D-扁桃酸脱氢酶(LhDMDH)和L-亮氨酸脱氢酶(EsLeuDH)偶联,在辅酶内循环的前提下,仅需较低浓度的辅酶即可实现生物催化D-扁桃酸合成L-苯甘氨酸。 通过对加酶量、氧化型烟酰胺腺嘌呤二核苷酸(NAD⁺)浓度、NH₄⁺浓度和底物浓度等因素进行优化,获得了一个最经济的反应条件:200 mmol/L的D-扁桃酸、6.5 kU/L的加酶量、0.1 mmol/L NAD⁺、0.5 mol/L NH₄⁺的条件下、30 ℃,反应12 h,在此条件下,产物的得率和对映体过量(e.e.)值分别可达98%和99%以上,具有较大的产业化潜力,为实现L-苯甘氨酸规模化的生物合成奠定了坚实的基础。     

用于手性识别α-氨基酸的方酰胺荧光探针分子

以天然氨基酸为手性原料合成了4种新型的手性方酰胺荧光探针分子(5~8), 该合成路线简短, 后处理简单, 无需柱层析纯化. 以荧光光谱为检测手段, 测试了此类探针分子对苯丙氨酸、 缬氨酸和脯氨酸的手性识别效果, 结果表明, 探针分子5可以有效识别苯丙氨酸的2个对映异构体. 当加入L-苯丙氨酸后, 探针分子5的荧光强度显著增强, 而加入D-苯丙氨酸后探针分子5的荧光强度显著减弱, 2种异构体的荧光强度比(I_L/I_D)可达2.4.     

水溶性手性Salen Mn(Ⅲ)的光谱性质及其对氨基酸客体的分子识别研究

合成并表征了手性配体Salen H₂及其锰配合物.详细讨论了配体及配合物的红外光谱、电子吸收光谱和圆二色光谱性质.研究结果表明,Salen Mn(Ⅲ)配合物在水溶液中为Δ构型,进一步证明了配合物中双偶氮螯环结构的确具有很高的刚性.用紫外-可见光谱滴定方法测定了锰配合物与氨基酸分子识别过程的缔合常数,实验结果表明:主体Salen Mn(Ⅲ)对每一对氨基酸对映异构体的识别能力均表现为对D-型的识别能力比对L-型大,对具有相同对映构型的不同氨基酸客体的识别能力按Phe, Val和Thr顺序依次递减.圆二色光谱(CD)考察结果与热力学研究结果一致.此外,采用分子力学方法考察了主客体体系的最低能量构象,并对该构象进行了量子化学计算,从理论上对实验事实作了进一步解释.     

手性温敏凝胶 P(NIPAM-co-NALL)的制备及识别性能

以L-亮氨酸(L-Leu)为手性源, 经酯化和缩合等步骤制备手性单体(NALL), 以该单体为手性识别基团, 在交联剂N,N'-亚甲基双丙烯酰胺和引发剂偶氮二异丁腈的作用下, 与N-异丙基丙烯酰胺(NIPAM)以不同的质量比发生自由基共聚, 制备了一系列新型手性温敏水凝胶P(NIPAM-co-NALL), 其结构经红外光谱确证. 相比于PNIPAM水凝胶, 疏水性单体NALL的引入使 P(NIPAM-co-NALL)凝胶的温敏性下降. 以D, L-苯丙氨酸为模型药物对P(NIPAM-co-NALL)凝胶的手性识别和拆分性能进行研究, 结果表明, 手性温敏凝胶对D型对映体具有选择吸附性, 且吸附量随着手性单体含量的增加而增加; 提高温度(40 ℃)有利于手性温敏凝胶对D, L-苯丙氨酸的手性识别和拆分. P(NIPAM-co-NALL)凝胶在重复使用后依然具有手性识别性能, 但其吸附量随着使用次数的增加而下降, 3次重复使用后吸附量下降到原来的27.6%.     

双相识别手性萃取佐匹克隆对映体动力学研究

以羟丙基-β-环糊精(HP-β-CD)和L-酒石酸异丁酯(L-IBTA)分别为水相和有机相中手性选择体构成双相识别手性萃取体系, 研究其对佐匹克隆(ZPC)对映体的萃取动力学. 分别考察了搅拌速度、两相接触面积、水相中ZPC对映体浓度、水相及有机相中手性选择体浓度以及水相pH值对ZPC对映体萃取动力学的影响. 结果表明, L-IBTA萃取ZPC对映体的反应为“快反应”|对ZPC对映体反应是一级反应, 对L-IBTA反应是二级反应|对R-ZPC和S-ZPC反应速率常数分别为31.25×10^－5和48.74×10^－5 mol^－2•m⁶•s^－1. 萃取速率随HP-β-CD浓度的增加而降低. 以上研究结果将为手性萃取的工程设计提供参考.     

低浓度下的仿生矿化及其在对映体拆分中的应用

以L-苯丙氨酸衍生物(L-18Phe6PyBr)的自组装体为模板, 在0.30 mmol/L的浓度下, 研究了pH值、 老化时间和四乙氧基硅烷(TEOS)浓度对二氧化硅形貌的影响. 通过扫描电子显微镜和透射电子显微镜对样品进行表征. 结果表明, 在pH=10.01的条件下可以得到左手扭转的纳米带, 而pH=7.15和12.34时, 得到直线的纳米带. 遵循动态模板的方法, 老化时间的延长有利于直线纳米带的形成. 随着TEOS和L-18Phe6PyBr的质量比由2:1增加到15:1, 扭转纳米带的宽度增加, 螺距变长. 通过煅烧除去有机模板后, 得到带状二氧化硅纳米管. 将TEOS与L-18Phe6PyBr质量比为2:1制备得到的二氧化硅作为气相色谱固定相, 涂渍到毛细管色谱柱中进行对映体拆分. 结果表明, 该气相色谱柱可以拆分1-苯基-1-丙醇、 1-(4-氯苯基)乙醇和2-甲基戊酸3种外消旋化合物, 手性超分子印迹是拆分对映体的主要作用力. 对二氧化硅低聚物与小分子凝胶的协同组装行为以及将无机材料作为手性固定相有了一个更好的认识.     

基于L/D-赖氨酸盐酸盐和光活化AIE分子共组装实现圆偏振发光及动态调控

近年来, 基于分子组装产生圆偏振发光(CPL)的有机手性材料得到了迅猛的发展. 然而, 目前有机材料体系的CPL信号整体仍然较弱, 且缺乏精准的调控手段. 为此, 本工作以具有光活性的聚集诱导荧光增强(AIE)性质的多硫苯基化合物(M-1)为荧光染料, 以手性氨基酸L/D-赖氨酸盐酸盐(L/D-Lys)为手性模板, 通过分子间氢键作用, 在N,N-二甲基甲酰胺(DMF)/H₂O的混合溶剂中形成超分子L/D-Lys@M-1共组装体. 共组装体在不良溶剂水的溶剂作用下诱导产生CPL, 且在紫外光激发下具有自聚集效应, 产生持续增强的荧光发射和圆二色(CD)信号. 通过荧光光谱、紫外吸收光谱和动态光散射(DLS)对组装体在光激发下的结构和光物理性质进行表征, 利用CD光谱以及CPL光谱等对基态和激发态手性性质进行研究. 结果表明, 在溶剂诱导和光激发下实现了L/D-Lys@M-1组装体的手性传递和放大, 且不对称因子(|g_lum|)达到了0.3×10^-2. 该研究策略为非手性的荧光分子构建CPL体系及动态调控提供了策略.     

基于手性大环主体的对映选择性识别

手性均一性是生命体系的基本物质结构特征,这导致手性对映体分子的识别和区分在许多与生命健康相关的领域都具有重要意义.大环主体是进行分子识别的重要工具,而通过构筑手性大环主体来实现对手性对映体客体的识别和区分一直是超分子化学研究的重要课题.近年来,随着大环主客体化学的蓬勃发展,基于手性大环主体的对映选择性识别也取得长足进步.本文概述了手性大环的常用构筑策略,并重点综述了具有代表性的手性大环主体以及它们的对映选择性识别能力,旨在激发具有优异对映选择性识别和区分能力的大环主体的开发和应用.最后总结了这一领域目前存在的挑战和发展前景.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.