acetyl 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranoside | 4356-77-8

• 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: acetyl 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: 1,6-di-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranoside；1,6-di-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranose；1,6-di-O-acetyl-2,3,4-tri-O-benzyl-D-α-glucose；O¹,O⁶-Diacetyl-O²,O³,O⁴-tribenzyl-α-D-glucopyranose；[(2R,3R,4S,5R,6R)-6-acetyloxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methyl acetate
• CAS: 4356-77-8
• 化学式: C₃₁H₃₄O₈
• 分子量: 534.606
• InChiKey: IFCAMEQHKHEHBS-SAEUYMBFSA-N

物化性质

• 熔点：
  64.0-65.5 °C
• 沸点：
  625.9±55.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  39
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  acetyl 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranoside 在 碘代三甲硅烷 、 4 A molecular sieve 、 四丁基碘化铵 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 3.0h， 生成 O-(6-O-Acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-(1->6)-1-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranose
  参考文献：
  名称：

  Solution-Phase Hexasaccharide Synthesis Using Glucosyl Iodides

  摘要：

  [GRAPHIC]Oligosaccharides composed of 1,6-glucosyl residues have been prepared from glucosyl iodides. The reactions are highly stereoselective, giving the a-glycosides as the only isolated products in yields ranging from 84% to 94%. Oligomer synthesis can take place in an iterative 1 + 1 + 1 fashion or in a convergent manner where dimer iodides serve as donors for higher order acceptors.

  DOI：

  10.1021/ol025887d
• 作为产物：
  描述：

  葡萄糖 在 sodium hydride 、 Selectfluor 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 27.67h， 生成 acetyl 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  A Novel Selectfluor-Mediated Regioselective O-Benzyl Ether Acetolysis of Perbenzylated Monosaccharides

  摘要：

  Selectfluor, a source of the super electrophile F+, has replaced conventional reagents that supply F+ for fluorination due to its attractive physical and chemical properties. This study is the first report of using Selectfluor as a debenzylating reagent. Selectfluor has been found to effect regioselective O- benzyl acetolysis from the per-O-benzylated derivatives of glucose and mannose, which are among the most commonly occurring monosaccharides. For both derivatives, one equivalent of Selectfluor first cleaves the primary benzyl, while a second equivalent subsequently removes the anomeric benzyl. Regioselective removal at higher equivalents proved difficult, with complex mixtures being obtained. The reaction proceeded under mild conditions with good yields and high regioselectivity, resulting in quick access to partially benzylated monosaccharide derivatives. This study provides shortened access to attractive building blocks for oligosaccharide synthesis.

  DOI：

  10.1080/07328303.2015.1108423

文献信息

• Enolic Ortho Esters. VI. A New 'Pyranose→Cyclohexane' Transformation via 1,6-Dideoxy-1,1-ethylenedioxy-2,3,4-tri-O-methyl-D-xylo-hex-5-enopyranose
  作者：DG Bourke、DJ Collins、AI Hibberd、MD Mcleod

  DOI：10.1071/ch9960425

  日期：——

  Hydrolysis of methyl 6-chloro-6-deoxy-2,3,4-tri-O-methyl-α-D-glucopyranoside (19b) and Swern oxidation of the resulting anomeric hemiacetals (20) gave 6-chloro-6-deoxy-2,3,4-tri-O-methyl-D-glucono-1,5-lactone (21), treatment of which with 1,2-bis( trimethylsilyloxy )ethane in the presence of trimethylsilyl trifluoromethanesulfonate gave 6-chloro-1,6-dideoxy-1,1-ethylenedioxy-2,3,4-tri-O-methyl-D-glucopyranose (23a). Conversion of (23a) into the corresponding 6-iodo compound (23b) and treatment of this with 1,8-diazabicyclo[5.4.0]undec-7-ene afforded the enolic ortho ester 1,6-dideoxy-1,1-ethylenedioxy-2,3,4-tri-O-methyl-D-xylo-hex-5-enopyranose (26). Reaction of (26) with methylmagnesium iodide, or with titanium tetrachloride, gave (1R,6S,7R,8R,9S)-7,8,9-trimethoxy-6-methyl-2,5-dioxabicyclo[4.3.1]decan-1-ol (34), or (2S,3R,4R)-5,5-ethylenedioxy-2,3,4-trimethoxycyclohexanone (28), respectively.

  水解 6-氯-6-脱氧-2,3,4-三-O-甲基-α-D-吡喃葡萄糖苷甲酯 (19b)，并将生成的异构半乙酸酯 (20) 斯韦尔恩氧化，得到 6-氯-6-脱氧-2,3,4-三-O-甲基-D-葡糖酸-1,5-内酯 (21)。 三氟甲磺酸三甲基硅酯的存在下，用 1,2-双（三甲基硅氧基）乙烷处理，得到 6-氯-1,6-二脱氧-1,1-亚乙二氧基-2,3,4-三-O-甲基-D-吡喃葡萄糖（23a）。将 (23a) 转化为相应的 6-碘化合物 (23b)，并用 1,8-二氮杂双环[5.4.0]十一-7-烯处理，可得到烯醇原酯 1,6-二脱氧-1,1-亚乙二氧基-2,3,4-三-O-甲基-D-氧代-己-5-烯吡喃糖 (26)。将 (26) 与甲基碘化镁或四氯化钛反应，分别得到 (1R,6S,7R,8R,9S)-7,8,9-三甲氧基-6-甲基-2,5-二氧杂环[4.3.1]癸烷-1-醇 (34) 或 (2S,3R,4R)-5,5-亚乙二氧基-2,3,4-三甲氧基环己酮 (28)。
• Regioselective Acetolysis of Highly<i>O</i>-Benzylated Carbohydrates Promoted by Iodine or an Iodine/Silane Combined Reagent: Use of Isopropenyl Acetate as an Alternative to Acetic Anhydride
  作者：Maddalena Giordano、Alfonso Iadonisi、Antonello Pastore

  DOI：10.1002/ejoc.201300064

  日期：2013.5

  the protocols presented here do not suffer from the use of harsh acidic reagents and excess amounts of high-boiling acetic anhydride. The activation of IPA with iodine and triethylsilane (or the cheaper polymethylhydrosiloxane, PMHS) usually results in shorter reaction times, with the acetolysis occurring preferentially (with some exceptions) at primary benzyloxy groups. With anomerically armed sugars

  聚-O-苄基化糖的区域选择性乙酰解脱-O-苄基化可以通过用碘/硅烷组合试剂或单独的碘激活乙酸异丙烯酯(IPA)来触发。与其他已知的乙酰化程序不同，此处介绍的协议不会受到使用强酸试剂和过量高沸点乙酸酐的影响。用碘和三乙基硅烷（或更便宜的聚甲基氢硅氧烷，PMHS）活化 IPA 通常会导致更短的反应时间，丙酮分解优先（有一些例外）发生在伯苄氧基。对于异头武装的糖，异头碘化可以是一个伴随的过程，以产生高反应性的中间体，在合适的淬火条件下，这些中间体可以原位转化为可用的和有用的结构单元。另一方面，单独用碘激活 IPA 可使反应在较温和的条件下发生，尽管时间较长。在几乎所有报道的例子中，IPA 可以适度过量使用（5 当量），但它作为溶剂的使用对于氨基糖模型化合物至关重要，否则对任何乙酰化修饰都是顽固的。这些条件的另一个优势在于前所未有的可能性，将乙酰化步骤纳入一锅合成序列，导致糖类底物的多种功能修饰。
• Rapid Synthesis of <scp>l</scp> -Idosyl Glycosyl Donors from α-Thioglucosides for the Preparation of Heparin Disaccharides
  作者：Mihály Herczeg、Fruzsina Demeter、Tímea Balogh、Viktor Kelemen、Anikó Borbás

  DOI：10.1002/ejoc.201800425

  日期：2018.7.6

  Synthesis of l‐idopyranosyl glycosyl donors starting from α‐ and β‐thio‐d‐glucopyranosides via the corresponding 5‐enopyranosides was studied for the first time. Hydroboration of the α‐configured 5‐enopyranosides proceeded with very high l‐ido stereoselectivity. After a 4,6‐O‐acetal formation, the obtained idosyl thioglycosides proved to be useful as donors in the synthesis of heparin‐related disaccharides

  的合成升-IDOpyranosyl糖基供体从α-和β硫代起始d -glucopyranosides经由相应的5- enopyranosides进行了研究，第一次。具有非常高的进行α-配置5- enopyranosides的硼氢化升- IDO立体选择性。在形成4,6- O-乙缩醛后，所获得的亚氨基磺酰糖苷被证明可作为肝素相关二糖合成的供体。
• Synthesis of methyl 6″-deoxy-6′-fluoro-α-isomaltoside and of the corresponding trisaccharide
  作者：Pavol Kováč、Vladimír Sklenář、Cornelis P.J. Glaudemans

  DOI：10.1016/0008-6215(88)84143-0

  日期：1988.5

  6-trimethylpyridine. O-Deacetylation of 5 , followed by treatment of the formed 6 , containing only HO-6′ unsubstituted, with diethylaminosulfur trifluoride (DAST) or dimethylaminosulfur trifluoride (methyl DAST) gave the per- O -benzyl derivative ( 9 ) of methyl 6′-deoxy-6′-fluoro-α-isomaltoside. Compound 9 was also obtained by condensation of 1 with 2,3,4-tri- O -benzyl-6-deoxy-6-fluoro-β- d -glucopyranosyl fluoride

  摘要甲基6-O-（6-O-乙酰基-2,3,4-三-O-苄基-α-d-吡喃葡萄糖基）-2,3,4-三-O-苄基-α-d-吡喃葡萄糖苷（当2,3,4-三-O-苄基-α-d-吡喃葡萄糖基（1）与6-O-乙酰基-2,3,4-三-O-苄基缩合时，形成具有高立体选择性的5）在2,4,6-三甲基吡啶存在下，用高氯酸银促进乙醚中的-α-d-吡喃葡萄糖基氯。5的O-脱乙酰化，然后用二乙基氨基三氟化硫（DAST）或二甲基氨基三氟化硫（甲基DAST）处理仅含未取代的HO-6'的生成的6，得到甲基6'的全-O-苄基衍生物（9） -脱氧-6'-氟-α-异麦芽糖苷。还可以通过1与2,3的缩合反应获得化合物9，在高氯酸银和无水氯化亚锡存在下的4-三-O-苄基-6-脱氧-6-氟-β-d-吡喃葡萄糖基氟（4）。通过将6与4缩合获得6-脱氧-6-氟-异麦芽三糖的完全苄基化的甲基α-糖苷（15）。9和15 gae的氢解异麦芽糖
• Total Synthesis of Alvaradoins E and F, Uveoside, and 10-epi-Uveoside
  作者：Kevin Ng、Ryan Shaktah、Laura Vardanyan、Thomas G. Minehan

  DOI：10.1021/acs.orglett.9b03546

  日期：2019.11.15

  Concise total syntheses of the anthracenone C-glycosides alvaradoins E and F, uveoside, and 10-epi-uveoside (1–4) have been accomplished from chrysophanic acid 8 and bromosugar 9. Key steps in the syntheses include the DBU-induced coupling of 8 and 9 to produce β-C-glycoside 11, and a Pb(OAc)4-mediated Kochi reaction to introduce the C-1′ oxygen atom of the natural products. Isothermal titration calorimetry

  的蒽酮的简洁全合成Ç -glycosides alvaradoins E和F，uveoside，和10表- uveoside（1 - 4）已从大黄酚完成8和bromosugar 9。合成的关键步骤包括DBU诱导的8和9偶联以产生β- C-糖苷11，以及Pb（OAc）4介导的高知反应以引入天然产物的C-1'氧原子。等温滴定热法和荧光结合研究表明，化合物1和2对血浆蛋白HSA具有良好的亲和力。