(2R,4aR,6S,8aS)-(+)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine | 65530-27-0

• 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: (2R,4aR,6S,8aS)-(+)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine
• 英文别名: methyl 4,6-O-benzylidene-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside；methyl-[O⁴,O⁶-((R)-benzylidene)-α-D-erythro-2,3-dideoxy-hex-2-enopyranoside]；Methyl-[O⁴,O⁶-((R)-benzyliden)-α-D-erythro-2,3-didesoxy-hex-2-enopyranosid]；(2R,4aR,6S,8aS)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine
• CAS: 65530-27-0
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: CULHEDOHPOHBOT-RFQIPJPRSA-N

物化性质

• 沸点：
  371.2±42.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,4aR,6S,8aS)-(+)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine 在 N-溴代丁二酰亚胺(NBS) 、 水 、 sodium hydride 作用下， 以 乙二醇二甲醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.33h， 生成 methyl 2,3-anhydro-4,6-O-benzilidene-α-D-mannopyranoside
  参考文献：
  名称：

  Tripyranoside precursors for ansamycins. Pyranosidic homologation. 6

  摘要：

  DOI：

  10.1021/jo00229a014
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2-O-p-tolylsulfonyl-3-deoxy-α-D-ribo-hexopyranoside 在 soda lime 作用下， 140.0 ℃ 、0.13 Pa 条件下， 生成 (2R,4aR,6S,8aS)-(+)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine
  参考文献：
  名称：

  3-脱氧d甘露糖。脱氧糖。第十一次沟通

  摘要：

  DOI：

  10.1002/hlca.19460290510

文献信息

• Allylic substitutions in tri-o-benzyl-glycals,4,6-o-benzylidene-glycals and related compounds
  作者：R.D.(Gus) Guthrie、Robert W. Irvine

  DOI：10.1016/s0008-6215(00)85699-2

  日期：1980.7

  3-unsaturated glycosyl azides. Similar reactions with derivatives of 4,6-O-benzylidene- d -allal and -glucal and with related 2,3-unsaturated analogues gave only azido-glycals. The mechanism of these reactions is discussed and compared with reactions of the tri-O-acetyl-glycals and related systems.

  摘要3,4,6-三-O-苄基-d-葡糖醛和4,6-二-O-苄基-2,3-二脱氧-己基-2-烯吡喃糖苷在三氟化硼催化下与叠氮化钠在乙腈中反应得到3-叠氮基-糖基和2，3-不饱和糖基叠氮化物的混合物。与4，6-O-亚苄基-d-alal和-glucal的衍生物以及与相关的2，3-不饱和类似物的类似反应仅产生叠氮基-糖基。对这些反应的机理进行了讨论，并将其与三-O-乙酰基缩醛和相关体系的反应进行了比较。
• A new and versatile method for the preparation of unsaturated sugars
  作者：Michel Bessodes、Elie Abushanab、Raymond P. Panzica

  DOI：10.1039/c39810000026

  日期：——

  Reaction of vicinal diols with iodoform, tri-phenylphosphine, and imidazole gives the corresponding olefin in high to moderate yields.

  邻位二醇与碘仿，三苯基膦和咪唑的反应以高到中等的产率得到相应的烯烃。
• Utilization of Sugars in Organic Synthesis. Part XXXIII. Thio-Sugars III. Radical Catalyzed Thione-Thiol Rearrangement of Cyclic Thionocarbonates on a Pyranose Ring: Formation of cis-Arranged Cyclic Thiolcarbonates.
  作者：Yoshisuke TSUDA、Shinsuke NOGUCHI、Kimihiro KANEMITSU、Yoshiyuki SATO、Kyoko KAKIMOTO、Yumiko IWAKURA、Shinzo HOSOI

  DOI：10.1248/cpb.45.971

  日期：——

  Pyranoside 3, 4-cis-thionocarbonates, under radical-promoted reaction conditions (method A, B, or C, described in the text), gave O-S rearrangement products, 3, 4-thiolcarbonates of cis-stereochemistry, in accepTable yields.2, 3-Thionocarbonates of trans-stereochemistry also gave the rearrangement products of cis-stereochemistry preferentially in method B (photolysis with hexabutyldistannane). Although regio-control of the product was not satisfactory in most cases, some of the results suggested that the regioselectivity of the reaction is markedly influenced by the stereochemistry of the anomeric position of the substrates. The products were converted to thioglycosides(peracetate forms) by conventional means.

  吡喃糖苷 3, 4-顺式硫代碳酸酯在自由基促进的反应条件下（方法 A、B 或 C，如本文所述）以可接受的产率生成 O-S 重排产物，即顺式立体化学的 3, 4-硫醇碳酸酯。2在方法B（用六丁基二锡烷光解）中，反式立体化学的3-硫代碳酸酯也优先产生顺式立体化学的重排产物。尽管在大多数情况下产物的区域控制并不令人满意，但一些结果表明反应的区域选择性明显受到底物异头位置的立体化学的影响。通过常规方法将产物转化为硫代糖苷（全乙酸盐形式）。
• An Efficient Stereoselective Dihydroxylation of Glycals using a Bimetallic System, RuCl₃/CeCl₃/NaIO₄
  作者：Pallavi Tiwari、Anup Kumar Misra

  DOI：10.1021/jo0526385

  日期：2006.3.31

  A catalytic dihydroxylation reaction on glycals has been developed using a bimetallic oxidizing system to furnish sugar 1,2-diols in a highly setreoselective manner.
• Intermolecular addition of epoxides to activated olefins: a new reaction
  作者：T. V. RajanBabu、William A. Nugent

  DOI：10.1021/ja00194a073

  日期：1989.6