tri(propan-2-yl)silyl 2-[(2S,4S,6S,8R,10S)-10-acetyloxy-2-[(3R,4S,5S)-4-acetyloxy-7-[(2R,4S,6R,8S,10S)-4-[tert-butyl(dimethyl)silyl]oxy-2-[(Z)-5-[(2R,3S,4S,6R)-4-[tert-butyl(dimethyl)silyl]oxy-6-methoxy-3-methyl-6-[(S)-[(2R,3S,4S)-3-methyl-4-triethylsilyloxy-3,4-dihydro-2H-pyran-2-yl]-triethylsilyloxymethyl]oxan-2-yl]pent-1-enyl]-10-methoxy-1,7-dioxaspiro[5.5]undecan-8-yl]-3,5-dimethyl-2-methylidene-6-oxoheptyl]-4-methyl-4-triethylsilyloxy-1,7-dioxaspiro[5.5]undecan-8-yl]acetate | 203516-63-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: tri(propan-2-yl)silyl 2-[(2S,4S,6S,8R,10S)-10-acetyloxy-2-[(3R,4S,5S)-4-acetyloxy-7-[(2R,4S,6R,8S,10S)-4-[tert-butyl(dimethyl)silyl]oxy-2-[(Z)-5-[(2R,3S,4S,6R)-4-[tert-butyl(dimethyl)silyl]oxy-6-methoxy-3-methyl-6-[(S)-[(2R,3S,4S)-3-methyl-4-triethylsilyloxy-3,4-dihydro-2H-pyran-2-yl]-triethylsilyloxymethyl]oxan-2-yl]pent-1-enyl]-10-methoxy-1,7-dioxaspiro[5.5]undecan-8-yl]-3,5-dimethyl-2-methylidene-6-oxoheptyl]-4-methyl-4-triethylsilyloxy-1,7-dioxaspiro[5.5]undecan-8-yl]acetate
• CAS: 203516-63-6
• 化学式: C₉₄H₁₇₆O₂₀Si₆
• 分子量: 1794.93
• InChiKey: IUTLAPNCGSJYAI-PQUKPLQRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  23.64
• 重原子数：
  120
• 可旋转键数：
  49
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  216
• 氢给体数：
  0
• 氢受体数：
  20

反应信息

• 作为反应物：
  描述：

  tri(propan-2-yl)silyl 2-[(2S,4S,6S,8R,10S)-10-acetyloxy-2-[(3R,4S,5S)-4-acetyloxy-7-[(2R,4S,6R,8S,10S)-4-[tert-butyl(dimethyl)silyl]oxy-2-[(Z)-5-[(2R,3S,4S,6R)-4-[tert-butyl(dimethyl)silyl]oxy-6-methoxy-3-methyl-6-[(S)-[(2R,3S,4S)-3-methyl-4-triethylsilyloxy-3,4-dihydro-2H-pyran-2-yl]-triethylsilyloxymethyl]oxan-2-yl]pent-1-enyl]-10-methoxy-1,7-dioxaspiro[5.5]undecan-8-yl]-3,5-dimethyl-2-methylidene-6-oxoheptyl]-4-methyl-4-triethylsilyloxy-1,7-dioxaspiro[5.5]undecan-8-yl]acetate 在 二甲基二环氧乙烷 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成
  参考文献：
  名称：

  Addition of allylstannanes to glycal epoxides. A diastereoselective approach to β-C-glycosidation

  摘要：

  A new method for the synthesis of beta-C-allyl glycosides has been developed for use in the synthesis of the spongipyran macrolides. Functionalized dihydropyrans are transformed to cia tetrahydropyrans via a two step process: i) epoxidation using dimethyldioxirane and ii) Lewis acid mediated epoxide opening with allylstannanes as nucleophiles. This protocol, which can be successfully applied to complex systems, augments the limited body of methodology available for the preparation of beta-configured C-glycosides. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00138-5
• 作为产物：
  描述：

  三异丙基氯硅烷 、 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以21.3 mg的产率得到tri(propan-2-yl)silyl 2-[(2S,4S,6S,8R,10S)-10-acetyloxy-2-[(3R,4S,5S)-4-acetyloxy-7-[(2R,4S,6R,8S,10S)-4-[tert-butyl(dimethyl)silyl]oxy-2-[(Z)-5-[(2R,3S,4S,6R)-4-[tert-butyl(dimethyl)silyl]oxy-6-methoxy-3-methyl-6-[(S)-[(2R,3S,4S)-3-methyl-4-triethylsilyloxy-3,4-dihydro-2H-pyran-2-yl]-triethylsilyloxymethyl]oxan-2-yl]pent-1-enyl]-10-methoxy-1,7-dioxaspiro[5.5]undecan-8-yl]-3,5-dimethyl-2-methylidene-6-oxoheptyl]-4-methyl-4-triethylsilyloxy-1,7-dioxaspiro[5.5]undecan-8-yl]acetate
  参考文献：
  名称：

  对映体全合成altohyrtin C（海绵抑素2）

  摘要：

  描述了海绵吡喃大环内酯的首个全合成，altohyrtinC。聚合合成策略依赖于区域选择性大内酯化，两个主要合成片段的立体选择性Wittig偶联，复杂的抗羟醛反应以连接C 1 –C 15和C 16 –C 28螺酮基区域，以及端基砜磺酰化以进行连接C 29 –C 37和C 38 –C 43吡喃区。C 44 –C 51的合并在合成的最后阶段，侧链为在该药理学重要区域中构建变体建立了可行的途径。方法的发展途中对总合成包括1,5-反-选择性甲基酮醇醛缩合反应和非对映选择性方法的路易斯酸介导的β - Ç -glycosidation。合成的完成证实了altohyrtin系列中提出的立体化学分配，并确定了altohyrtin和海绵体抑素海洋大环内酯类的身份。

  DOI：

  10.1016/s0040-4020(99)00438-x

文献信息

• Enantioselective Synthesis of Altohyrtin C(Spongistatin 2): Fragment Assembly and Revision of the Spongistatin 2 Stereochemical Assignment
  作者：David A. Evans、B. Wesley Trotter、Bernard Côté、Paul J. Coleman、Luiz Carlos Dias、Andrew N. Tyler

  DOI：10.1002/anie.199727441

  日期：1997.1.7