methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-α-D-altro-pyranoside | 68907-47-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-α-D-altro-pyranoside
• 英文别名: Methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-α-D-altropyranoside；4,6-O-benzylidene-2-deoxy-2-C-methyl-α-D-altropyranoside；(2R,4aR,6S,7S,8S,8aS)-6-methoxy-7-methyl-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• CAS: 68907-47-1
• 化学式: C₁₅H₂₀O₅
• 分子量: 280.321
• InChiKey: LTIJSBJNBACWEN-LKAWMXSOSA-N

物化性质

• 沸点：
  436.1±45.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-α-D-altro-pyranoside 在 咪唑 、 2,3,5-三甲基吡啶 、 甲醇 、 4-二甲氨基吡啶 、 palladium diacetate 、 sodium tetrahydroborate 、 草酰氯 、 四溴化碳 、 三氟甲磺酸三甲基硅酯 、 2,4,6-三氯苯甲酰氯 、 2,4,6-三异丙基苯磺酰基肼 、 1,3-双(二苯基膦)丙烷 、 potassium tert-butylate 、 水 、 四丁基醋酸铵 、 二甲基二环氧乙烷 、 sodium hydride 、 对甲苯磺酸 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 三氟乙酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 32.0h， 生成 埃博霉素B
  参考文献：
  名称：

  Synthesis of epothilones B and D from d-glucose

  摘要：

  An enantiospecific total synthesis of epothilones B and D from, D-glucose is reported. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00457-4

文献信息

• Diastereoselective [2,3] Wittig rearrangement of carbohydrate-derived tertiary allylic ethers. 2. Synthesis of an advanced rapamycin intermediate from D-glucose.
  作者：Ny Sin、James Kallmerten

  DOI：10.1016/0040-4039(93)89003-9

  日期：1993.1

  The advanced rapamycin intermediate 26 has been prepared by an iterative sigmatropic sequence incorporating the diastereoselective [2,3] Wittig rearrangement of a D-glucofuranose-derived tertiary allylic ether.

  先进的雷帕霉素中间体26已通过合并包含D-葡萄糖呋喃糖衍生的叔烯丙基醚的非对映选择性[2,3] Wittig重排的迭代sigmatropic序列进行制备。
• Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors
  作者：Florence Chéry、Stéphanie Cassel、Hans Peter Wessel、Patrick Rollin

  DOI：10.1002/1099-0690(20021)2002:1<171::aid-ejoc171>3.0.co;2-7

  日期：2002.1

  We introduce a convenient synthesis of anomeric sulfimides, the ability of which to act as glycosyl donors has been tested with various thiophilic reagents and acceptors.

  我们介绍了一种方便的异头磺酰亚胺合成方法，其作为糖基供体的能力已经用各种亲硫试剂和受体进行了测试。
• The Carbohydrate-Sesquiterpene Interface. A Zirconocene-Mediated Synthesis­ of (+)-Epiafricanol from <scp>d</scp>-Glucose
  作者：Leo Paquette、Ruslan Arbit、Jacques-Alexis Funel、Sergei Bolshakov

  DOI：10.1055/s-2002-34380

  日期：——

  A total synthesis of (+)-epiafricanol (6) has been readily achieved from d-glucose. The tricyclic alcohol target was arrived at by first forming methyl 6-O-benzyl-2-deoxy-2-C-methyl-α-d-altropyranoside (12) and converting this intermediate into methyl 2-C-methyl-2,3,4-trideoxy-α-d-threo-hexopyranoside (14). There followed a series of steps resulting in extension of the side chain to give the isopropenyl pyranoside 9. This advanced intermediate was subjected to zirconocene-promoted ring contraction, which gave rise to 8 and set the stage for conversion to 7. This tertiary carbinol was transformed into 6 by sequential ring-closing metathesis and stereodirected Simmons-Smith cyclopropanation.

  (+)-epiafricanol (6) 很容易从 d-葡萄糖中完全合成。 首先形成甲基 6-O-苄基-2-脱氧-2-C-甲基-δ-d-altropyranoside (12)，然后将该中间体转化为甲基 2-C-甲基-2,3,4-三脱氧-δ-±-d-苏-吡喃糖苷 (14)，从而达到三环醇的目标。经过一系列步骤，侧链得到延伸，从而得到异丙烯基吡喃糖苷 9。这种高级中间体经过锆碳烯促进的环收缩，产生了 8，为转化成 7 创造了条件。通过连续的闭环偏析和立体定向 Simmons-Smith 环丙烷化反应，这种三级甲醇被转化为 6。
• Sialyl aldolase in organic synthesis: from the trout egg acid 3-deoxy-D-glycero-D-galacto-2-nonulosonic acid (KDN) to branched-chain higher ketoses as possible new chirons.
  作者：Claudine Augé、Christine Gautheron、Serge David、Annie Malleron、Bertrand Cavayé、Bénédicte Bouxom

  DOI：10.1016/s0040-4020(01)97593-3

  日期：1990.1

  N-Acetylneuraminate pyruvate lyase accepts as substrates varied non-nitrogeneous sugars. Condensation of pyruvate with D-mannose yields 3-deoxy-D-glycero-D-galacto-2-nonulosonic acid (KDN) a component of rainbow trout egg polysialoglycoprotein. From some easily available monosaccharides were prepared other ulosonic acids: 3-deoxy-D-galacto-2-octulosonic 35dideoxy-D-gluco-2-nonulosonic and 37-dideo

  N-乙酰神经氨酸丙酮酸裂解酶接受各种非氮源糖作为底物。丙酮酸与D-甘露糖的缩合产生3-脱氧-D-甘油-D-半乳糖-2-壬基磺酸（KDN），它是虹鳟鱼卵多唾液酸糖蛋白的一种成分。从一些容易得到的单糖制备其它ulosonic酸：3-脱氧-D-半乳-2-辛酮糖35dideoxy-D-葡糖-2- nonulosonic和37二脱氧D-半乳-2- nonulosonic酸。葡萄糖不是良好的底物，D-阿拉伯糖产生了预期的3-脱氧-D-葡萄糖的混合物-2-辛基磺酸（19％）和3-脱氧-D-甘露糖-2-辛基磺酸（16％）。后者是来自细菌多糖的众所周知的糖酸KDO，其是由缩合步骤中的异常取向导致的。通过保留2-脱氧-2- C -2-苯基-D-的76％收率的转化，证明了酶对糖的C（2）处的取代基的性质的相对冷漠，只要保留了D-甘露聚糖构型即可。甘露糖转化成35-二脱氧-5 - C-苯基-D-葡萄糖-2-壬基磺
• Synthesis of sugar-based ethenyl ethers through a vinyl bis-sulfone methodology
  作者：Florence Chéry、Matthieu Desroses、Arnaud Tatibouët、Ottorino De Lucchi、Patrick Rollin

  DOI：10.1016/s0040-4020(03)00661-6

  日期：2003.6

  The recently devised route to ethenyl ethers-i.e. 1,2-bis(phenylsulfonyl)ethylene (BPSE)-mediated conversion of alcohols into beta-alkoxyvinyl sulfones followed by reductive desulfonylation-has been applied in the carbohydrate field to the synthesis of a number of vinyl-functionalised monosaccharides, a number of which had not been prepared via alternative routes. (C) 2003 Elsevier Science Ltd. All rights reserved.