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1.
报道了双恶唑啉和Schiff碱二类手性配合物的合成及其在光学活性菊酸的不对称合成中的应用,以合成氯霉素中间体的无效体(1S,2S)-2-氨基-1-对硝基苯基-1,3-丙二醇为原料,分别制得了二取代双恶唑啉和Schiff碱二类配体,并将其分别与醋酸铜配合后得到手性铜催化剂来诱导烯烃(2,5-二甲基-2,4-己二烯和1,1-二苯乙烯)与重氮乙酸酯的不对称环丙烷化反应,最高获得45.2%e.e。 相似文献
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以2-羟基蒎烷-3-酮(1)与氨基乙腈缩合得到的手性酮亚胺(2)为中间体,经去质子化,在Pd(0)催化下与1,4-二氯-2-丁烯(3)发生串联反应,得到光学活性环丙烷衍生物(4),产率约为70%,反应的非对映立体选择性(d.e.)为100%.化合物4经选择性还原后水解,即可制得光学活性2-乙基环丙烷氨基酸,产物的对映体过量(e.e.)为33%. 相似文献
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以( - )1 R,2 S2氨 基1 ,2二苯 基乙 醇 作为 手性 源, 与取 代 水杨 醛 缩合 制 备 了系 列 手性 Schiff 碱配 体,考察 了该类配体的二价铜配合物及配体与 Cu( C H3 C N)4 Cl O4 组成的原位 体系对2 ,5二甲基2 ,4己二烯与 重氮乙酸 L薄 荷酯的环丙烷化反应的催化作用. 结果表明, Cu(Ⅱ) 配合物尽管具有较高的催化活性,但几乎没有光 学选择性,而原 位体系 则表 现出极 高的 催化活 性和 一定的 光学选择性,化学收率为903 % , 顺 式体e .e .值达到30 % 相似文献
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在自制的硅基纤维素-三(3,5-二甲基苯基氨基甲酸酯)高效液相色谱手性固定相上(HPLC-CSP),优化了1-(6'-甲氧基萘)乙醇氢酯基化反应产物-萘普生甲酯手性分离的条件,测定了相应的一系列不对称氢酯基化反应产物的对映体过剩值(e.e.值)。结果表明,在CDMPC-CSP手性柱上用HPLC测定此类不对称催化反应的光学产率,评价催化剂体系的手性选择是一种非常理想的方法。 相似文献
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本文采用pH法,在25.0±0.1℃,I=0.1mol·dm-3KNO3存在条件下,测定了铜(Ⅱ)-1,4,7,10-四氮杂环十三烷-11,13-二酮-α-氨基酸(5-取代邻菲罗啉)三元配合物的稳定常数,探讨了大环多胺配体与金属离子的配位能力、配位方式、及其在水溶液中铜(Ⅱ)配合物的稳定性,同时也研究了5-取代邻菲罗啉与铜(Ⅱ)之间的d-p反馈π键、取代基的Hammett诱导效应对三元配合物稳定性的影响. 相似文献
8.
苏桂发 《高等学校化学学报》1998,19(8):1256-1261
以2-羟基蒎烷-3-酮(1)与氨基乙腈缩合得到的手怀酮亚胺(2)为中间体,经去质子化,在Pd(0)催化下与1,4-二氯-2-丁烯(3)发生串联反应,得到光学活性环丙烷衍生物(4),产率约为70%,反应的非对映立体选择性(d.e.)为100%,化全物4经选择性学原后水解,即可制得光学活性2-乙基环丙烷氨基酸,产物的对映体过量(e.e.)为33%。 相似文献
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报道从D-甘露醇出发合成手性双膦(2S,5S)-3,6-双(二苯膦)-1,4:3,6-双脱水-2,5-双去氧-L-艾杜醇,原位下BDPI与3种铑配合物作用生成手性非螯合型双膦铑催化剂,常压下对4种脱氢苯丙氨酸衍生物进行不对称催化化反主尖,对反应结果及e.e.值进行了讨论。 相似文献
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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%. 相似文献
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Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction
Laurent Gavara Thomas Boisse Jean-Pierre Hénichart Adam Daïch Philippe Gautret 《Tetrahedron》2010,66(38):7544-5571
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. 相似文献
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Uroš Grošelj Mojca Žorž Amalija Golobič Branko Stanovnik Jurij Svete 《Tetrahedron》2013,69(52):11092-11108
A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives. 相似文献
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The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp3)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp2)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp2)?H and aliphatic 1,5- and 1,6-C(sp3)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp3)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp2)?H insertion. 相似文献
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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. 相似文献
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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. 相似文献
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Rebecca J. Burton Mandy L. CrowtherNeal J. Fazakerley Shaun M. FilleryBarry M. Hayter Jason G. KettleCaroline A. McMillan Paula PerkinsPeter Robins Peter M. SmithEmma J. Williams Gail L. Wrigley 《Tetrahedron letters》2013
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. 相似文献
18.
N. A. Nedolya 《Chemistry of Heterocyclic Compounds》2008,44(10):1165-1219
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. 相似文献
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N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%). 相似文献
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Shashikant U. Dighe Surya K. Samanta Shivalinga Kolle Sanjay Batra 《Tetrahedron》2017,73(17):2455-2467
An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y1 and Y2. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones. 相似文献