tert-butyl-[(Z)-6-[tert-butyl(dimethyl)silyl]oxyhex-5-enoxy]-diphenylsilane | 160557-86-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tert-butyl-[(Z)-6-[tert-butyl(dimethyl)silyl]oxyhex-5-enoxy]-diphenylsilane
• CAS: 160557-86-8
• 化学式: C₂₈H₄₄O₂Si₂
• 分子量: 468.827
• InChiKey: AWMBJQNLZROTPY-QJOMJCCJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.27
• 重原子数：
  32
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl-[(Z)-6-[tert-butyl(dimethyl)silyl]oxyhex-5-enoxy]-diphenylsilane 在 2,6-二甲基吡啶 、 lithium allyl oxide 、 barium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 98.17h， 生成 (1R,4S,5R,6R)-4,6-Bis-(tert-butyl-dimethyl-silanyloxy)-5-[4-(tert-butyl-diphenyl-silanyloxy)-butyl]-cyclohex-2-ene-1,1-dicarboxylic acid allyl ester methyl ester
  参考文献：
  名称：

  Stereocontrolled Total Synthesis of Calcitriol Derivatives: 1,25-Dihydroxy-2-(4'-hydroxybutyl)vitamin D3 Analogs of an Osteoporosis Drug

  摘要：

  The diastereomeric 2 alpha- and 2 beta-(4'-hydroxybutyl) calcitriol analogs (-)-3 and (+)-3' were prepared in only 11 chemical operations, starting with 4 + 2-cycloaddition of commercially available methyl 2-pyrone-3-carboxylate. Highlights of this convergent and stereocontrolled synthetic approach are as follows: (1) retention of reactant dienophile geometry in the product bicyclic lactone, characteristic of a concerted inverse-electron-demand Diels-Alder cycloaddition; (2) an improved decarboxylation procedure involving chemospecific allyloxide opening of a lactone ring in the presence of a methyl ester and then non-high pressure palladium-promoted allylic ester decarboxylation; and (3) use of the enantiomercially pure C,D-ring chiron (+)-14 to resolve racemic A-ring phosphine oxide (+/-)-13. Relative binding affinities of the enantiomerically pure diastereomers (-)-3 and (+)-3' to the vitamin D binding protein and to the vitamin D receptor showed some unexpected trends. Diastereomer (+)-3' surprisingly bound more effectively to the vitamin D receptor than did the established osteoporosis drug ED-71 (1).

  DOI：

  10.1021/jo00104a050
• 作为产物：
  描述：

  6-{[tert-butyl(diphenyl)silyl]oxy}hexan-1-ol 在 dipyridine chromium trioxide 、 三乙胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 2.0h， 生成 tert-butyl-[(Z)-6-[tert-butyl(dimethyl)silyl]oxyhex-5-enoxy]-diphenylsilane
  参考文献：
  名称：

  Stereocontrolled Total Synthesis of Calcitriol Derivatives: 1,25-Dihydroxy-2-(4'-hydroxybutyl)vitamin D3 Analogs of an Osteoporosis Drug

  摘要：

  The diastereomeric 2 alpha- and 2 beta-(4'-hydroxybutyl) calcitriol analogs (-)-3 and (+)-3' were prepared in only 11 chemical operations, starting with 4 + 2-cycloaddition of commercially available methyl 2-pyrone-3-carboxylate. Highlights of this convergent and stereocontrolled synthetic approach are as follows: (1) retention of reactant dienophile geometry in the product bicyclic lactone, characteristic of a concerted inverse-electron-demand Diels-Alder cycloaddition; (2) an improved decarboxylation procedure involving chemospecific allyloxide opening of a lactone ring in the presence of a methyl ester and then non-high pressure palladium-promoted allylic ester decarboxylation; and (3) use of the enantiomercially pure C,D-ring chiron (+)-14 to resolve racemic A-ring phosphine oxide (+/-)-13. Relative binding affinities of the enantiomerically pure diastereomers (-)-3 and (+)-3' to the vitamin D binding protein and to the vitamin D receptor showed some unexpected trends. Diastereomer (+)-3' surprisingly bound more effectively to the vitamin D receptor than did the established osteoporosis drug ED-71 (1).

  DOI：

  10.1021/jo00104a050

文献信息

• Stereocontrolled Total Synthesis of Calcitriol Derivatives: 1,25-Dihydroxy-2-(4'-hydroxybutyl)vitamin D3 Analogs of an Osteoporosis Drug
  作者：Gary H. Posner、Neil Johnson

  DOI：10.1021/jo00104a050

  日期：1994.12

  The diastereomeric 2 alpha- and 2 beta-(4'-hydroxybutyl) calcitriol analogs (-)-3 and (+)-3' were prepared in only 11 chemical operations, starting with 4 + 2-cycloaddition of commercially available methyl 2-pyrone-3-carboxylate. Highlights of this convergent and stereocontrolled synthetic approach are as follows: (1) retention of reactant dienophile geometry in the product bicyclic lactone, characteristic of a concerted inverse-electron-demand Diels-Alder cycloaddition; (2) an improved decarboxylation procedure involving chemospecific allyloxide opening of a lactone ring in the presence of a methyl ester and then non-high pressure palladium-promoted allylic ester decarboxylation; and (3) use of the enantiomercially pure C,D-ring chiron (+)-14 to resolve racemic A-ring phosphine oxide (+/-)-13. Relative binding affinities of the enantiomerically pure diastereomers (-)-3 and (+)-3' to the vitamin D binding protein and to the vitamin D receptor showed some unexpected trends. Diastereomer (+)-3' surprisingly bound more effectively to the vitamin D receptor than did the established osteoporosis drug ED-71 (1).