(2R,4aR,6S,7S,8S,8aS)-6-methoxy-7-methyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine | 109958-35-2

• 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,7S,8S,8aS)-6-methoxy-7-methyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 109958-35-2
• 化学式: C₂₂H₂₆O₅
• 分子量: 370.445
• InChiKey: YSZVIAGEFRBPAP-UUKSMCIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,4aR,6S,7S,8S,8aS)-6-methoxy-7-methyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine 在 4-二甲氨基吡啶 、 对甲苯磺酸 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 2-[(2R,3R,4S,5S,6S)-3-hydroxy-6-methoxy-5-methyl-4-phenylmethoxyoxan-2-yl]acetonitrile
  参考文献：
  名称：

  Synthetic Studies toward Ciguatoxin. Stereocontrolled Construction of the KLM Ring Fragment

  摘要：

  The first stereoselective synthesis of the KLM ring fragment of ciguatoxin is reported including as a key step 7-endo selective cyclization of epoxy alcohol to construct a fully substituted oxepane ring (12 --> 13).

  DOI：

  10.1021/jo00083a008
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-α-D-altro-pyranoside 、 溴甲苯 在 sodium hydride 作用下， 生成 (2R,4aR,6S,7S,8S,8aS)-6-methoxy-7-methyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
  参考文献：
  名称：

  有机合成中的唾液酸醛缩酶：从鳟鱼卵酸3-脱氧-D-甘油-D-半乳糖-2-壬基磺酸（KDN）到支链高级酮糖，尽可能的是新的chirons。

  摘要：

  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

  DOI：

  10.1016/s0040-4020(01)97593-3

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。
• 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
• Synthetic Studies toward Ciguatoxin. Stereocontrolled Construction of the KLM Ring Fragment
  作者：Makoto Sasaki、Masayuki Inoue、Kazuo Tachibana

  DOI：10.1021/jo00083a008

  日期：1994.2

  The first stereoselective synthesis of the KLM ring fragment of ciguatoxin is reported including as a key step 7-endo selective cyclization of epoxy alcohol to construct a fully substituted oxepane ring (12 --> 13).
• Chapleur, Yves; Boquel, Pascal; Chretien, Francoise, Journal of the Chemical Society. Perkin transactions I, 1989, p. 703 - 705
  作者：Chapleur, Yves、Boquel, Pascal、Chretien, Francoise

  DOI：——

  日期：——
• Stereocontrolled Synthesis of the JKLM Ring Fragment of Ciguatoxin
  作者：Makoto Sasaki、Masayuki Inoue、Kuniyuki Takamatsu、Kazuo Tachibana

  DOI：10.1021/jo990988j

  日期：1999.12.1

  A highly stereocontrolled synthesis of the JKLM ring fragment of ciguatoxin has been achieved. The present synthesis starts with methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-a-D whose configurations and substituents at C2-C5 correspond to those at C46-C49 of ciguatoxin, and involves as the key step base-induced 7-endo selective cyclization of a hydroxy epoxide for the efficient construction of the fully substituted oxepane ring K. Construction of the spiroether ring M was achieved by introduction of an allyl group to the ring L lactone followed by asymmetric dihydroxylation to install the C54 stereogenic center and acid-induced spiroketalization to furnish the protected KLM ring system. Finally, ring J was constructed by the method of Nicolaou to complete the synthesis of the JKLM ring fragment. The synthesis of a carboxylic acid derivative and its conjugation to carrier proteins to give an artificial antigen for development of an immunoassay system for the parent toxin molecule are also reported.