1-O,2-S-(2-acetyl-1-methyl-1,2-ethenediyl)-3,4,6-tri-O-benzyl-2-thio-α-D-glucopyranose | 152420-91-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-O,2-S-(2-acetyl-1-methyl-1,2-ethenediyl)-3,4,6-tri-O-benzyl-2-thio-α-D-glucopyranose
• 英文别名: 1-[(4aR,6R,7R,8S,8aR)-3-methyl-7,8-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-6,7,8,8a-tetrahydro-4aH-pyrano[2,3-b][1,4]oxathiin-2-yl]ethanone
• CAS: 152420-91-2
• 化学式: C₃₂H₃₄O₆S
• 分子量: 546.684
• InChiKey: AXWGFRIGTHQRCM-DDBRSFKJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  39
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-O,2-S-(2-acetyl-1-methyl-1,2-ethenediyl)-3,4,6-tri-O-benzyl-2-thio-α-D-glucopyranose 在 三氟甲磺酸 、 3 A molecular sieve 、 四氯化钛 、 镍 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 19.5h， 生成 methyl 3,4,6-tri-O-benzyl-2-deoxy-D-glucopyranoside
  参考文献：
  名称：

  Novel Bicylic Donors for the Synthesis of 2-Deoxy-β-Glycosides

  摘要：

  Novel bicyclic glycosyl donors have been prepared by the cycloaddition reaction of glycals with 3-thiono-2,4-pentanedione 17 followed by methylenation of the resulting ketone. Treatment of the heterocyclic donors with triflic acid in the presence of a variety of alcohol accepters leads to the formation of beta-glycosides in good yields and with excellent stereoselectivities. Desulfurization of the C-2 carbon-sulfur bonds gives the corresponding 2-deoxy-beta-glycosides. This method has been extended to the synthesis of glycosidic linkages found in the aureolic acid antibiotics. Tetra-N-butylammonium triflate proved to be a useful additive in these glycosylation reactions, suggesting an important role for triflate anion in stabilizing intermediates which are formed.

  DOI：

  10.1021/jo971934h
• 作为产物：
  描述：

  D-葡萄烯糖 在 2,6-二甲基吡啶 、 3 Angstroem MS 、 四丁基溴化铵 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 1-O,2-S-(2-acetyl-1-methyl-1,2-ethenediyl)-3,4,6-tri-O-benzyl-2-thio-α-D-glucopyranose
  参考文献：
  名称：

  Novel Heterocycloaddition Reaction of Glycals

  摘要：

  Diacyl thione species 1 has been generated and reacted in situ with both pyranoid and furanoid glycals to form novel [4 + 2] cycloadducts. Factors such as protecting groups and configuration of substituents in the glycals along with medium effects were varied to discover influences on face selectivity and reactivity. A qualitative correlation of reactivity with the HOMO-LUMO gap between the glycal (HOMO) and the heterodienic species (LUMO) is observed. In one example, the isolation of byproducts suggests that the cycloaddition may in fact be stepwise.

  DOI：

  10.1021/jo981047u

文献信息

• Phthalimidesulfenyl chloride part 6. The First Example of an α-oxothione acting as heterodiene: Synthesis of 2,3-dihydro-1,4-oxathiines.
  作者：Giuseppe Capozzi、Stefano Menichetti、Cristina Nativi、Alessandro Rosi、Richard W. Franck

  DOI：10.1016/s0040-4039(00)60541-5

  日期：1993.6

  α-α'-Dioxothione 3a acts as heterodiene undergoing 4+2 cycloaddition reactions with enol ethers with the regiospecific formation of 2,3-dihydro-1,4-oxathiines 5 in good yields. The reaction is very simple and quite general. Using this reaction the thiosugar derivative 5e has been also prepared.

  α-α'-二氧杂环丁烷3a用作异二烯，与烯醇醚进行4 + 2环加成反应，并以良好的产率形成2,3-二氢-1,4-氧杂亚砜5的区域特异性形成。该反应非常简单并且非常笼统。使用该反应，还制备了硫糖衍生物5e。
• Stereoselective 2-Deoxy-β-O-glycoside Synthesis Based on Remote Activation of Novel Oxathiine Donors
  作者：Alessandra Bartolozzi、Giuseppe Capozzi、Stefano Menichetti、Cristina Nativi

  DOI：10.1002/1099-0690(200106)2001:11<2083::aid-ejoc2083>3.0.co;2-t

  日期：2001.6

  1-glycals and 3-thioxopentane-2,4-dione, have been transformed into unusual glycosyl donors which, after “remote activation”, react efficiently with glycosyl acceptors to afford 2-thio-β-O-glycosides with total stereoselectivity. Several O-nucleophiles were successfully glycosylated. Reductive removal of sulfur transformed the 2-thio-β-O-glycosides into the corresponding 2-deoxy-β-O-glycosides without affecting

  通过合适的 1-glycals 和 3-thioxopentane-2,4-dione 之间的逆电子需求 Diels-Alder 反应制备的稳定的糖融合 1,4-oxathiine 衍生物已转化为不寻常的糖基供体，在“远程激活后” ”，与糖基受体有效反应以提供具有总立体选择性的 2-硫代-β-O-糖苷。几个O-亲核试剂被成功地糖基化。硫的还原去除将 2-硫代-β-O-糖苷转化为相应的 2-脱氧-β-O-糖苷，而不影响异头碳原子的立体化学。
• Versatile intermediate for complete α/β stereocontrol in O-glycosidation reactions
  作者：Giuseppe Capozzi、Francesca Mannocci、Stefano Menichetti、Cristina Nativi

  DOI：10.1039/a705338j

  日期：——

  β-O-Glucosides 5, which can be completely converted to the α-anomers in the reaction medium, are obtained as single isomers by glycosidation of readily available donor 1 and are easily transformed into 2-deoxy-β-O-glucosides.

  δ-O-葡萄糖苷 5 可在反应介质中完全转化为δ-异构体，它是通过对容易获得的供体 1 进行糖苷化反应而获得的单一异构体，并很容易转化为 2-脱氧-δ-O-葡萄糖苷。
• Phthalimidesulfenyl Chloride. 9. A Simple Access to .alpha.,.alpha.'-Dioxothiones, a New Class of Bis-heterodienes. Synthesis of 1,4-Oxathiin Systems
  作者：G. Capozzi、R. W. Franck、M. Mattioli、S. Menichetti、C. Nativi、G. Valle

  DOI：10.1021/jo00125a030

  日期：1995.10

  alpha,alpha'-Dioxothiophthalimides 4a and 4b react with pyridine to generate the alpha,alpha'-dioxothiones 5a and 5b which undergo chemo- and regiospecific inverse electron demand Diels-Alder reactions With electron-rich alkenes to give 1,4-oxathiin heterocyclic systems. Enol ethers, silyl enol ethers, vinyl sulfides, vinyl amides, substituted styrenes, and electron rich alkynes and allenes can be fruitfully employed as dienophiles. Among the vinyl ethers tested tri-O-benzylglucal was successfully used as a dienophile. Ab initio molecular orbital calculations performed on thiones 5a and 5b as well as on a selected enol ether are consistent with the experimental results. When thione 5a was generated in the presence of 2,3-dimethyl-2-butene (31) and -(beta)-pinene (33) a selective ''thiophlic ene reaction'' was observed leading to the formation of sulfides 32 and 34. Thione 5b reacted similarly with 33 to generate the sulfide 35. Additionally a competition between the dienic versus dienophilic behavior of alpha,alpha'-dioxothiones 5a and 5b was observed in reactions with 2,3-dimethoxy-1,3-butadiene (45) and 2-methoxyfuran (50). A preliminary screening of the reactivity of 1,4-oxathiins 7c and 8b, used as model substrates, is also outlined.
• Recent advances in the synthesis of 2-deoxy-glycosides
  作者：Dianjie Hou、Todd L. Lowary

  DOI：10.1016/j.carres.2009.07.013

  日期：2009.10

  Glycosides of 2-deoxy-sugars, monosaccharides in which the hydroxyl group at C-2 is replaced with a hydrogen atom, occur widely in natural products and therefore have been the subject of intense synthetic activity. The report summarizes recent advances in this area, with a particular focus on work published since an earlier review on the topic, in 2000 (Marzabadi, C. H.: Franck, R. W. Tetrahedron 2000, 56, 8385-8417). (C) 2009 Elsevier Ltd. All rights reserved.