4-[2-(tert-butyl-diphenyl-silanyloxy)-ethylidene]-2-triisopropylsilanyloxymethyl-6-trityloxymethyl-tetrahydropyran | 184174-44-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 4-[2-(tert-butyl-diphenyl-silanyloxy)-ethylidene]-2-triisopropylsilanyloxymethyl-6-trityloxymethyl-tetrahydropyran
• 英文别名: tert-butyl-diphenyl-[(2Z)-2-[(2R,6S)-2-[tri(propan-2-yl)silyloxymethyl]-6-(trityloxymethyl)oxan-4-ylidene]ethoxy]silane
• CAS: 184174-44-5
• 化学式: C₅₃H₆₈O₄Si₂
• 分子量: 825.292
• InChiKey: VPWPQALRCQCGJS-JJSXUKTNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.24
• 重原子数：
  59
• 可旋转键数：
  18
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  4-[2-(tert-butyl-diphenyl-silanyloxy)-ethylidene]-2-triisopropylsilanyloxymethyl-6-trityloxymethyl-tetrahydropyran 在 六甲基磷酰三胺 、 2,6-二叔丁基-4-甲基吡啶 、 四丁基氟化铵 、 叔丁基锂 、 溶剂黄146 、 zinc dibromide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 50.83h， 生成 2-[6-(2-(tert-butyl-dimethyl-silanyloxy)-3-{2-[4-(2-hydroxy-ethylidene)-6-hydroxymethyl-tetrahydro-pyran-2-ylmethyl]-[1,3]dithian-2-yl}-3-methyl-butyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-ethanol
  参考文献：
  名称：

  Asymmetric Synthesis of the Northern Half C1−C16 of the Bryostatins

  摘要：

  [GRAPHICS]Starting from 8-oxabicyclo[3.2.1]oct-6-en-3-one and racemic 2,2-dimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one the C1-C16 segment of the bryostatins has been synthesized in 30 steps and 9% overall yield (17 steps longest linear sequence), Fragment coupling by dithiane strategy and protecting group manipulations provided an advanced chemodifferentiated northern half segment.

  DOI：

  10.1021/ol015551o
• 作为产物：
  描述：

  (2-triisopropylsilanyloxymethyl-6-trityloxymethyl-tetrahydropyran-4-ylidene)-acetic acid isopropyl ester 在 咪唑 、 二异丁基氢化铝 作用下， 以 正己烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 2.5h， 生成 4-[2-(tert-butyl-diphenyl-silanyloxy)-ethylidene]-2-triisopropylsilanyloxymethyl-6-trityloxymethyl-tetrahydropyran
  参考文献：
  名称：

  Asymmetric Synthesis of the Northern Half C1−C16 of the Bryostatins

  摘要：

  [GRAPHICS]Starting from 8-oxabicyclo[3.2.1]oct-6-en-3-one and racemic 2,2-dimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one the C1-C16 segment of the bryostatins has been synthesized in 30 steps and 9% overall yield (17 steps longest linear sequence), Fragment coupling by dithiane strategy and protecting group manipulations provided an advanced chemodifferentiated northern half segment.

  DOI：

  10.1021/ol015551o

文献信息

• Enantioselective Formal Total Synthesis of the Antitumor Macrolide Bryostatin 7
  作者：Soraya Manaviazar、Mark Frigerio、Gurpreet S. Bhatia、Marc G. Hummersone、Abil E. Aliev、Karl J. Hale

  DOI：10.1021/ol061626i

  日期：2006.9.1

  A new enantioselective synthesis of Masamune's AB fragment (1) for bryostatin 7 is described. Key steps in the new route include a Meerwein-Ponndorf-Verley reduction to set the O(7) stereocenter and an alkylative union between the dithiane 6 and iodide 5 to construct the C(9)-C(10) bond. Because we have previously published a synthesis of Masamune's C-ring phenyl sulfone 2, our new route to 1 constitutes

  描述了新的Masamune的AB片段（1）对bryostatin 7的对映选择性合成。新路线中的关键步骤包括Meerwein-Ponndorf-Verley还原以设置O（7）立体中心，以及在二噻吩6和碘化物5之间形成C（9）-C（10）键的烷基键合。因为我们之前已经发表过Masamune的C环苯基砜2的合成方法，所以我们新的1路线构成了bryostatin 7的正式总合成；它还可以校正先前报告的CDCl3中1的光谱数据。