p-chlorophenyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-1-thiohex-2-enopyranoside | 240418-68-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: p-chlorophenyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-1-thiohex-2-enopyranoside
• 英文别名: p-chlorophenyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio-α-D-erythro-hex-2-enopyranoside；((3S)-3-acetoxy-6-((4-chlorophenyl)thio)-3,6-dihydro-2H-pyran-2-yl)methyl acetate；[(2R,3S,6R)-3-acetyloxy-6-(4-chlorophenyl)sulfanyl-3,6-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 240418-68-2
• 化学式: C₁₆H₁₇ClO₅S
• 分子量: 356.827
• InChiKey: VTNKMRWISZYNJF-ARFHVFGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  87.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4-氯苯硫酚 、 乙酰化葡萄烯糖 在 碘 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以90%的产率得到p-chlorophenyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-1-thiohex-2-enopyranoside
  参考文献：
  名称：

  Highly Stereoselective Synthesis of 2,3-Unsaturated Thioglycopyranosides Employing Molecular Iodine

  摘要：

  首次利用分子碘实现了d-甘露二糖型糖类的硫代糖基化反应，与各种硫醇反应以高产率得到相应的2,3-不饱和硫代糖苷。在三-O-乙酰基-d-甘露二糖型糖类的情况下，仅获得了α-异构体。由于使用了易获得的碘，这种方法非常简单、便捷且实用。

  DOI：

  10.1055/s-0029-1218722

文献信息

• 3,5-Dinitrobenzoic acid catalyzed synthesis of 2,3-unsaturated O- and S-glycosides and tetrahydropyranylation of alcohols and phenols
  作者：Naganjaneyulu Bodipati、Srinivasa Rao Palla、Venkateshwarlu Komera、Rama Krishna Peddinti

  DOI：10.1016/j.tetlet.2014.10.093

  日期：2014.12

  A simple procedure for the synthesis of 2,3-unsaturated glycosides in acetonitrile and tetrahydropyranylation of alcohols and phenols in dichloromethane in the presence of 3,5-dinitrobenzoic acid is described. A variety of alcohols and thiols are reacted with glycals to give the desired products in high yields with high α-selectivity.

  描述了一种简单的程序，用于在乙腈中合成2,3-不饱和糖苷以及在3,5-二硝基苯甲酸存在下在二氯甲烷中将醇和酚进行四氢吡喃基化。使多种醇和硫醇与缩醛反应，以高收率和高α选择性得到所需产物。
• Diastereoselective Synthesis of Thioglycosides via Pd-Catalyzed Allylic Rearrangement
  作者：Jiagen Li、Ming Wang、Xuefeng Jiang

  DOI：10.1021/acs.orglett.1c03302

  日期：2021.12.3

  palladium-catalyzed allylic rearrangement yields various substituents on α-isomer thioglycosides. Two comprehensive series of aryl and benzyl thioglycosides were obtained via a combination of thiosulfates with glycals derived from glucose, arabinose, galactose, and rhamnose. Furthermore, diosgenyl α-l-rhamnoside and isoquercitrin achieved selectivity via stereospecific [2,3]-sigma rearrangements of α-sulfoxide-rhamnoside

  立体选择性糖基化在碳水化合物化学中具有挑战性。在此，通过钯催化的烯丙基重排对糖醛进行立体选择性硫代糖基化，可在 α-异构体硫糖苷上产生各种取代基。通过硫代硫酸盐与衍生自葡萄糖、阿拉伯糖、半乳糖和鼠李糖的糖苷的组合，获得了两个综合系列的芳基和苄基硫糖苷。此外，薯蓣基 α-l-鼠李糖苷和异槲皮苷分别通过 α-亚砜-鼠李糖苷和 α-亚砜-葡萄糖苷的立体特异性 [2,3]-σ 重排实现了选择性。
• 不饱和硫苷化合物及其选择性合成方法与应用
  申请人：华东师范大学

  公开号：CN113651863A

  公开（公告）日：2021-11-16

  本发明公开了一种选择性合成式(II)α‑硫苷化合物、式(III)β‑硫苷化合物的合成方法，在反应溶剂中，以三乙酰葡萄糖烯为反应原料，以不同取代基的有机硫代硫酸盐为硫源，在金属钯盐、配体的作用下，选择性合成α‑硫苷化合物(II)、β‑硫苷化合物(III)。本发明所述的合成方法，原料易得价廉，反应操作简单，反应条件温和，产率较高，官能团耐受优秀。本发明实现了一些复杂分子的合成与修饰，为药物化学的研究提供了选择性构建含有不饱和键硫苷化合物的高效方法。
• Ferrier rearrangement promoted by an electrochemically generated zirconium catalyst
  作者：Dragana Stevanović、Anka Pejović、Ivan Damljanović、Aleksandra Minić、Goran A. Bogdanović、Mirjana Vukićević、Niko S. Radulović、Rastko D. Vukićević

  DOI：10.1016/j.carres.2015.02.001

  日期：2015.4

  In situ generated zirconium catalyst from a sacrificial zirconium anode was successfully applied to promote Ferrier rearrangement of 3,4,5-tri-O-acetyl-D-glucal and 6-deoxy-3,4-di-O-acetyl-L-glucal (3,4-di- O-acetyl-L-rhamnal) in the presence of three thiols and eleven thiophenols as nucleophiles. A simple constant current electrolysis (20 mA, 0.4 F mol(-1)) of an acetonitrile solution of lithium perchlorate (0.1 M) containing the corresponding glycal and S-nucleophiles, using a zirconium anode and a platinum cathode resulted in the successful synthesis of the corresponding 2,3-unsaturated peracetylated thioglycosides (with an average anomer ratio alpha/beta-4.129 in the case of peracetylated D-glucal and 8.740 in the case of L-rhamnal). The same procedure proved to be appropriate in synthesizing dihydropyran derivatives ('C-glycosides') using allyltrimethylsilane as the nucleophile (only 'alpha-anomers' were obtained). All new compounds were fully characterized by spectral data, whereas single-crystal X-ray analysis was performed for two thioglycosides. (C) 2015 Elsevier Ltd. All rights reserved.
• Ruthenium Catalyzed Stereo/Chemo/Regioselective One-Pot Synthesis of C(2)–C(3) Unsaturated and α-<scp>d</scp>-Mannopyranosyl Sulfones
  作者：Sravanthi Chittela、Thurpu Raghavender Reddy、Palakodety Radha Krishna、Sudhir Kashyap

  DOI：10.1021/acs.joc.5b00975

  日期：2015.7.17

  An efficient and divergent approach to C(2)-C(3) unsaturated glycosyl and a-p-mannopyranosyl sulfones has been developed via ruthenium-promoted direct glycosylation, oxidation, and dihydroxylation from glycal in one-pot. The presence of stoichiometric amounts of NaIO4 and in situ generation of RuO4 from a RuCl3-NaIO4 reagent system were crucial for chemoselective oxidation of sulfide in the presence of an olefin moiety. The dual-role of ruthenium in sequential glycosylation-oxidation-dihydroxylation is amenable to a wide range of thio acceptors to access alpha-n-mannopyranosyl sulfones in good yields with high regioselectivity.