3,4,6-tri-O-acetyl-α-D-glucopyranose-1,2-(t-butylorthoacetat) | 4715-05-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4,6-tri-O-acetyl-α-D-glucopyranose-1,2-(t-butylorthoacetat)
• 英文别名: 3,4,6-tri-O-acetyl-1,2-O-tert-butylorthoacetyl-α-D-glucopyranose；Tri-O-acetyl-3,4,6(tert-butylorthoacetyl-1,2)α-D-glucopyranose；[(3aR,5R,6R,7S,7aR)-6,7-diacetyloxy-2-methyl-2-[(2-methylpropan-2-yl)oxy]-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl acetate
• CAS: 4715-05-3
• 化学式: C₁₈H₂₈O₁₀
• 分子量: 404.414
• InChiKey: CPHHOBDQMIXIDV-ALHXCHNJSA-N

物化性质

• 熔点：
  152-154 °C
• 沸点：
  448.8±45.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-α-D-glucopyranose-1,2-(t-butylorthoacetat) 在 2,4,6-三甲基吡啶高氯酸盐 甲醇 、 氢氧化钾 作用下， 以 氯仿 为溶剂， 生成 12β,25-Di-β-D-glycopyranosyloxy-20(S),24(R)-epoxydammaran-3α-ol
  参考文献：
  名称：

  Glycosylation of triterpenoids of the dammarane series. II. 12,25-di-O- and 3,12,25-tri-o-glucopyranosides of 20(S), 24 (R)-epoxydammarane-3α, 12β, 25-triol and its 3-epimer

  摘要：

  DOI：

  10.1007/bf00568513
• 作为产物：
  描述：

  叔丁醇 、 β-D-葡萄糖五乙酸酯 在 三氯化铝 、 4-二甲氨基吡啶 作用下， 以 氯仿 为溶剂， 反应 26.75h， 以89%的产率得到3,4,6-tri-O-acetyl-α-D-glucopyranose-1,2-(t-butylorthoacetat)
  参考文献：
  名称：

  Syntheses of phosphatidyl-β-d-glucoside analogues to probe antigen selectivity of monoclonal antibody ‘DIM21’

  摘要：

  Herein, we report the chemical syntheses of a series of phosphatidyl-beta-D-glucoside (PtdGlc) analogues, including 6-O-Ac, sn-2-O-Me, phosphorothioate as well as phosphatidylgalactoside and -mannoside derivatives. In the key step, beta-glycosyl H-phosphonate was condensed with enantiomerically pure diacylglycerol. Comparison of spectroscopic data with mono-acetylated PtdGlc from natural source confirmed the presence of an acetyl moiety at position 6. Furthermore, the reactivity of PtdGlc and its analogues toward monoclonal antibody 'DIM21' (MAb DIM21) was evaluated, revealing the crucial structural antigen features for successful MAb DIM21 binding. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2008.06.041

文献信息

• Glycosylation of triterpenoids of the dammarane series. IV. ?-D-glucopyranosides of betulafolienetriol and its derivatives
  作者：L. N. Atopkina、V. A. Denisenko、V. L. Novikov、N. I. Uvarova

  DOI：10.1007/bf00598297

  日期：——

  The glycosylation of betulafolienetriol (dammar-24-ene-3α,12β,20(S)-triol) under the conditions of the Koenigs-Knorr, the Helferich, and the orthoester methods has been studied. It has been shown that the condensation of β-folienetriol and its 3-epimer with α-acetobromoglucose in the presence of silver oxide leads to a mixture of the corresponding 3-, 12-, and 20-mono- and 3,12- and 3,20-di-O-β-pD-glucopyranosides

  已经研究了在 Koenigs-Knorr、Helferich 和原酸酯方法条件下桦木三醇 (dammar-24-ene-3α,12β,20(S)-triol) 的糖基化。已经表明，在氧化银存在下，β-亚叶三醇及其 3-差向异构体与 α-乙酰溴葡萄糖的缩合会产生相应的 3-、12- 和 20- 单-和 3,12- 和3,20-di-O-β-p​​D-吡喃葡萄糖苷。已经确定 dammar-24-ene-3α,12β,20(S)-triol 在 Helferich 条件下和原酸酯法的糖基化伴随着侧链脱水的副反应并导致 20-脱羟基衍生物。所有新获得的化合物的结构都是根据红外光谱和 1 H 和 13 C NMR 光谱的结果确定的。
• Synthesis, Cytotoxic Activity Evaluation and Quantitative Structure-ActivityAnalysis of Substituted 5,8-Dihydroxy-1,4-naphthoquinones and Their O- and S-Glycoside Derivatives Tested against Neuro-2a Cancer Cells
  作者：Sergey Polonik、Galina Likhatskaya、Yuri Sabutski、Dmitry Pelageev、Vladimir Denisenko、Evgeny Pislyagin、Ekaterina Chingizova、Ekaterina Menchinskaya、Dmitry Aminin

  DOI：10.3390/md18120602

  日期：——

  increase in the cytotoxic activity of acetylated thioglycosidesof NQs, which was partially retained for their deacetylated derivatives. Thiomethylglycosides of 2-hydroxy-1,4-NQs with OH and MeO groups in quinone core at positions 6 and 7, resprectively formed a nontoxic set of compounds with EC50 > 100 μM. A quantitative structure-activity relationship (QSAR) model of cytotoxic activity of 22 1,4-NQ derivatives

  基于源自海胆的6,7-取代的2,5,8-三羟基-1,4-萘醌（1,4-NQs），制备了五种新的NQs乙酰-O-葡萄糖苷。开发了一种通过亚甲基间隔基将过O-乙酰化的1-巯基糖与2-羟基-1,4-NQ偶联的新方法。重氮甲烷使乙酰硫基甲基糖苷的醌核心的2-羟基甲基化和糖部分的脱乙酰基导致28个新的2-羟基-和2-甲氧基-1,4-NQs的硫代甲基糖苷。通过MTT方法测定了起始的1，4-NQs（13种化合物）及其O-和S-糖苷衍生物（37种化合物）对Neuro-2a小鼠神经母细胞瘤细胞的细胞毒活性。具有EC 50的细胞毒性化合物= 2.7–87.0μM ，发现EC 50 > 100μM的无毒化合物。乙酰化的O-和S-糖苷1,4-NQ最有效，EC 50 = 2.7-16.4μM。2-OH基萘醌核心的甲基化导致NQs的乙酰化硫糖苷的细胞毒活性急剧增加，而NQs的乙酰化硫糖苷部分保留了它们的脱乙酰基衍生物。2-羟基-1
• Synthesis of acetylated glycosides of hydroxynaphthoquinones
  作者：S. G. Polonik、A. M. Tolkach、N. I. Uvarova

  DOI：10.1007/bf00579766

  日期：——

  A method is proposed for the synthesis of acetylated glycosides of hydroxynaphthoquinones. The condensation of D-glucose and D-galactose (tert-butyl orthoacetate)s with lawsone and lapachol has given the tetra-O-acetyl-β-D-glucopyranosides of lawsone and of lapachol and the tetra-O-acetyl-β-galactopyranoside of lawsone. The structures of the glycosides obtained have been confirmed by IR and1H and13C

  提出了一种合成羟基萘醌的乙酰化糖苷的方法。D-葡萄糖和 D-半乳糖（原乙酸叔丁酯）与 Lawsone 和 Lapachol 的缩合得到了 Lawsone 和 Lapachol 的四-O-乙酰基-β-D-吡喃葡萄糖苷和四-O-乙酰基-β-劳松的吡喃半乳糖苷。所得糖苷的结构已通过IR和1H和13C NMR光谱证实。先前描述的lawone 乙酰半乳糖苷的结构已得到纠正。
• An environmentally benign and practical synthesis of sugar orthoesters promoted by potassium fluoride
  作者：Shin-ichiro Shoda、Masashi Moteki、Ryuko Izumi、Masato Noguchi

  DOI：10.1016/j.tetlet.2004.09.175

  日期：2004.11

  An extremely practical method for synthesis of sugar orthoesters has been developed without using any organic amines or heavy metals as additives. Various sugar orthoesters were prepared in good yields by the reaction of an acylated glycosyl bromide and an alcohol in the presence of potassium fluoride.

  已经开发了一种非常实用的糖原酸酯合成方法，无需使用任何有机胺或重金属作为添加剂。通过在氟化钾存在下酰化的糖基溴化物和醇的反应以高收率制备各种糖原酸酯。
• Structures of Side Products from Helferich Reaction Synthesis of 3α,12β,25-Trihydroxy-20S,24R-Epoxydammarane Glucosides
  作者：L. N. Atopkina、V. A. Denisenko

  DOI：10.1007/s10600-014-0824-0

  日期：2014.1

  Glycosylation of 3α-acetoxy-12β,25-dihydroxy-20S,24R-epoxydammarane (2) by 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosylbromide (5) in the presence of Hg(CN)2 in nitromethane at 22°C produced the acetylated 12,25-di-O-β-D-glucopyranoside of 3α,12β,25-trihydroxy-20S,24R-epoxydammarane (6) and also formed the side product 3α-acetoxy-12β-(2′,3′,4′,6′-tetra-O-acetyl-β-D-glucopyranosyloxy)-24-cyano-20S,24S-epoxydammarane (8). Condensation of 3α,12β-diacetoxy-25-hydroxy-20S,24R-epoxydammarane (3) with glycosyl donor (5) under the same conditions gave the hexaacetate of the 25-O-β-D-glucopyranoside of 3α,12β,25-trihydroxy-20S,24R-epoxydammarane and also formed a mixture of C-24-epimers (1:1) of 3α,12β-diacetoxy-24-cyano-20S,24ξ-epoxydammarane (10a,b).

  2,3,4,6-etra-O-acetyl-α-D-glucopyranosylbromide (5) 在 Hg(CN)2 的存在下，于 22°C 在硝基甲烷中对 3α-乙酰氧基-12β,25-二羟基-20S,24R-环氧达玛烷 (2) 进行糖基化，生成乙酰化的 12、25-二-O-β-D-吡喃葡萄糖苷的 3α,12β,25-三羟基-20S,24R-环氧达玛烷 (6)，并生成副产物 3α-乙酰氧基-12β-(2′,3′,4′,6′-四-O-乙酰基-β-D-吡喃葡萄糖氧基)-24-氰基-20S,24S-环氧达玛烷 (8)。在相同条件下，3α,12β-二乙酰氧基-25-羟基-20S,24R-环氧达玛烷（3）与糖基供体（5）缩合，得到了 3α,12β,25-三羟基-20S,24R-环氧达玛烷的 25-O-β-D-吡喃葡萄糖苷的六乙酸酯，还形成了 C-24 表聚物的混合物（1：1）的 3α，12β-二乙酰氧基-24-氰基-20S，24ξ-环氧达玛烷（10a，b）的混合物。