共查询到20条相似文献,搜索用时 15 毫秒
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药物中多数使用的为低于50个原子组成的有机小分子,这些小分子中很多具有手性,药理作用是药物小分子通过与体内大分子之间严格手性匹配识别实现的。手性亚砜作为重要的手性中间体、手性配体、辅剂、催化剂和手性药物,光学纯度的手性亚砜是很多药物的活性基团,所以对潜手性的硫醚的不对称催化氧化以达到高光学纯度是具备重大意义的。本文对钛催化硫醚氧化及其相关体系作简要的介绍,然后再进一步介绍亚砜作为药物方面的应用。 相似文献
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Armando Crdova Shuangzheng Lin Abrehet Tseggai 《Advanced Synthesis \u0026amp; Catalysis》2012,354(7):1363-1372
A general strategy for the total asymmetric synthesis of valuable tropane alkaloids by catalytic stereoselective transformations is disclosed. The power of this approach is exemplified by the concise catalytic enantioselective total syntheses of (+)‐methylecgonine, (−)‐cocaine and (+)‐cocaine as well as the first catalytic asymmetric total syntheses of a cocaine C‐1 derivative and (+)‐ferruginine starting from 5‐oxo‐protected‐α,β‐unsaturated enals using only two and three column chromatographic purification steps, respectively. 相似文献
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合成了一系列单磺酰化手性二胺,并用于催化丙酮与对硝基苯甲醛的不对称羟醛缩合反应。研究了手性二胺以及磺酰基结构对反应的影响,也研究了添加剂对反应的影响。对催化剂进行筛选,发现对硝基苯磺酰基取代的(1 S,2 S)-1,2-二苯基乙二胺为最佳催化剂,采用苯甲酸作为添加剂,反应可取得中等收率与对映选择性。 相似文献
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二烷基锌对醛的不对称加成反应是合成手性二级醇的有效方法,反应产物手性二级醇是药物、精细化学品、天然产物的重要中间体,手性氨基醇是诱导这类反应手性配体的重要组成部分并且表现出了很高的对映选择性。综述了催化该类反应手性氨基醇配体的一些研究新进展。 相似文献
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Yang Wang Man‐Su Tu Feng Shi Shu‐Jiang Tu 《Advanced Synthesis \u0026amp; Catalysis》2014,356(9):2009-2019
The first catalytic asymmetric construction of the biologically important dibenzo[1,4]diazepine scaffold has been established via SPINOL‐derived chiral phosphoric acid‐catalyzed three‐component reactions of aldehydes, 1,2‐phenylenediamines and cyclohexane‐1,3‐diones, which afforded structurally complex and diverse dibenzo[1,4]diazepines in high yields and good enantioselectivities (up to 98% yield, 92:8 er). This transformation also represents the first catalytic asymmetric version of this three‐component reaction and provides an easy access to structurally rigid seven‐membered chiral heterocycles.
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手性亚砜是重要的手性中间体和辅剂、手性配体和催化剂、手性药物。手性金属络合物催化硫醚的不对称氧化是合成手性亚砜最有效的方法。文章简要的介绍了钛,钒,铌,铁四种金属的络合物不对称催化硫醚氧化的一些最新的研究现状。 相似文献
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Easy stereoselective oxidation of prochiral aryl alkyl sulfides 2 to the corresponding sulfoxides can be achieved in water‐surfactant medium with inexpensive hydrogen peroxide mediated by the chiral platinum diphosphine complex {[(R)‐BINAP]Pt(μ‐OH)}2(BF4)2 ( 1 ). Remarkable key features of general interest are (i) easy isolation of the products from catalyst by simple diethyl ether/water‐surfactant two phase separation, (ii) catalyst loading as low as 1% mol, (iii) good yields, sulfoxide 3 to sulfone 4 ratio up to 200 : 1 and enantioselectivities up to 88%, (iv) mild experimental conditions. 相似文献
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Milnacipran and analogues are conveniently prepared by a short sequence of steps from phenylacetic acid, the key step being highly enantioselective catalytic asymmetric cyclopropanation. 相似文献
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The chiral benzofuranone structural motif is a prominent feature in many natural products, which exhibit a broad range of biological and pharmaceutical activities. In the past few years, a survey of chiral benzofuranone derivatives based on asymmetric catalysis reveals an increasing number of papers, which reflects the latest achievements to facilitate the synthesis of sufficient quantities of related compounds as potential medicinal agents and biological probes. Recent advances in this area are summarized and classified according to the structure of the starting substrate.
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《Journal of Sulfur Chemistry》2013,34(3):301-341
This review discusses synthesis of enantiopure sulfoxides through the asymmetric oxidation of prochiral sulfides. The use of metal complexes to promote asymmetric sulfoxidation is described in detail, with a particular emphasis on the synthesis of biologically active sulfoxides. The use of non-metal-based systems, such as oxaziridines, chiral hydroperoxides and peracids, as well as enzyme-catalyzed sulfoxidations is also examined. 相似文献
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Qingle Zeng Heqing Wang Tongjian Wang Yimin Cai Wen Weng Yufen Zhao 《Advanced Synthesis \u0026amp; Catalysis》2005,347(15):1933-1936
Simple, inexpensive, preformed vanadium‐Schiff base complexes were facilely prepared and used in enantioselective sulfoxidation. Both the amount of aqueous H2O2 and reaction time greatly influenced the ee values and yields of chiral sulfoxides. High enantioselectivities (up to 99% ee) and reasonable yields (>40%) for various chiral sulfoxides were achieved by combining enantioselective sulfoxidation and appropriate concomitant kinetic resolution. 相似文献
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Yujiro Hayashi Junichiro Yamaguchi Kazuhiko Hibino Tatsunobu Sumiya Tatsuya Urushima Mitsuru Shoji Daisuke Hashizume Hiroyuki Koshino 《Advanced Synthesis \u0026amp; Catalysis》2004,346(12):1435-1439
trans‐4‐tert‐Butyldimethylsiloxy‐L ‐proline displays a greater catalytic activity than the parent proline without compromising the enantioselectivity, which widens the substrate scope in the α‐aminoxylation of carbonyl compounds, as well as O‐nitroso‐aldol/Michael, and Mannich reactions. 相似文献
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Zhao‐Min Liu Hua Zhao Mei‐Qiu Li Yu‐Bao Lan Qi‐Bo Yao Jing‐Chao Tao Xing‐Wang Wang 《Advanced Synthesis \u0026amp; Catalysis》2012,354(6):1012-1022
(R)‐1,1′‐Binaphthyl‐2,2′‐diol (R‐BINOL) derived chiral phosphoric acids have been explored as organocatalysts for the asymmetric oxidation of a series of aryl alkyl sulfides and 1,3‐dithianes derived from aldehydes with aqueous hydrogen peroxide (H2O2) as the terminal oxidant. The enantiomerically enriched sulfoxides are obtained in moderate to excellent yield (up to 99%) with excellent diastereoselectivity (up to >99:1 dr) and moderate to good enantioselectivity (up to 91:9 er). In particular, the present protocol stereoselectively provides an efficient access to enantiomerically enriched aryl alkyl sulfoxides and dithioacetal mono‐sulfoxides, which strictly restrains the formation of the undesirable by‐products: sulfones or disulfoxides. The tracking experiments also verify that this approach proceeds via a direct sulfoxidation process, instead of a kinetic resolution route by overoxidation of the resulting sulfoxides. 相似文献
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Tao Song Long‐Sheng Zheng Fei Ye Wen‐Hui Deng Yun‐Long Wei Ke‐Zhi Jiang Li‐Wen Xu 《Advanced Synthesis \u0026amp; Catalysis》2014,356(8):1708-1718
An interesting group of multifunctional phosphines (Ar‐BINMOL‐Phos; Ar‐BINMOL=1,1′‐binaphthalene‐2‐α‐arylmethanol‐2′‐ol) with multi‐stereogenic centers of axial and sp3‐central chirality has been prepared successfully from a single chiral source through a concise synthetic route, in which the neighbouring lithium‐promoted [1,2]‐Wittig rearrangement proceeding with excellent diastereoselectivity and enantioselectivity is the key process in this approach. Also, in the catalytic alkynylation of aromatic aldehydes with terminal alkynes, the combination of these Ar‐BINMOL‐Phos ligands with dimethylzinc was found to be an effective catalyst system to afford predominantly the S‐configured propargylic alcohols, whereas the additional use of calcium hydride and n‐butyllithium along with the same Ar‐BINMOL‐Phos ligands gave the R‐configured products in high yields and excellent enantioselectivities (up to >99% ee).