2,2-Dimethyl-butyric acid (1R,5S,6R,8S,9S,10S,11S)-10-{2-[(2R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-6-oxo-tetrahydro-pyran-2-yl]-ethyl}-6,11-dimethyl-3,3,3-triphenyl-2,4-dioxa-3λ5-phospha-tricyclo[7.4.0.01,5]tridec-8-yl ester | 134004-77-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2,2-Dimethyl-butyric acid (1R,5S,6R,8S,9S,10S,11S)-10-{2-[(2R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-6-oxo-tetrahydro-pyran-2-yl]-ethyl}-6,11-dimethyl-3,3,3-triphenyl-2,4-dioxa-3λ5-phospha-tricyclo[7.4.0.01,5]tridec-8-yl ester
• 英文别名: 2,2-Dimethyl-butyric acid (1R,5S,6R,8S,9S,10S,11S)-10-{2-[(2R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-6-oxo-tetrahydro-pyran-2-yl]-ethyl}-6,11-dimethyl-3,3,3-triphenyl-2,4-dioxa-3λ⁵-phospha-tricyclo[7.4.0.0^1,5]tridec-8-yl ester
• CAS: 134004-77-6
• 化学式: C₄₉H₆₉O₇PSi
• 分子量: 829.142
• InChiKey: LZHINTBEUJQYSH-IHNSGHLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.43
• 重原子数：
  58.0
• 可旋转键数：
  11.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  80.29
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-butyric acid (1R,5S,6R,8S,9S,10S,11S)-10-{2-[(2R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-6-oxo-tetrahydro-pyran-2-yl]-ethyl}-6,11-dimethyl-3,3,3-triphenyl-2,4-dioxa-3λ5-phospha-tricyclo[7.4.0.01,5]tridec-8-yl ester 在 水 作用下， 反应 16.0h， 生成 2,2-Dimethyl-butyric acid (1S,3R,7S,8S,8aR)-8-{2-[(2R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-6-oxo-tetrahydro-pyran-2-yl]-ethyl}-4-hydroxy-3,7-dimethyl-1,2,3,5,6,7,8,8a-octahydro-naphthalen-1-yl ester
  参考文献：
  名称：

  Novel synthesis of mevinolin-related compounds. Large-scale preparation of HMG-CoA reductase inhibitor L-679,336

  摘要：

  A novel synthetic route to a mevinolin-related HMG-CoA reductase inhibitor L-679,336 is described. The key features of the synthesis are a diastereoselective osmium tetraoxide catalyzed dihydroxylation reaction and a highly selective, phosphorus-mediated, pinacol-type rearrangement to give ketone 6. In situ multinuclear NMR experiments were used to gain a detailed understanding of the pinacol step. The above route was used for multikilogram preparation of the title compound. Also described are Lewis acid catalyzed rearrangement reactions of epoxide intermediates 4 and 5, as well as the intramolecular hydrosilylation reaction of deacylated olefinic substrates 17 and 18.

  DOI：

  10.1021/jo00011a022
• 作为产物：
  描述：

  6(R)-<2-<8(S)-<(2,2-dimethylbutyryl)oxy>-2(S),6(R)-dimethyl-1,2,3,4,6,7,8,8a(R)-octahydronaphthyl-1(S)>ethyl>-4(R)-<(tert-butyldimethylsilyl)oxy>-3,4,5,6-tetrahydro-2H-pyran-2-one 在 吡啶 、 四氧化锇 、 十二/十四烷基二甲基氧化胺 、 水 、 N,N-二异丙基乙胺 作用下， 以 氘代乙腈 、 丙酮 为溶剂， 反应 21.5h， 生成 2,2-Dimethyl-butyric acid (1R,5S,6R,8S,9S,10S,11S)-10-{2-[(2R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-6-oxo-tetrahydro-pyran-2-yl]-ethyl}-6,11-dimethyl-3,3,3-triphenyl-2,4-dioxa-3λ5-phospha-tricyclo[7.4.0.01,5]tridec-8-yl ester
  参考文献：
  名称：

  Novel synthesis of mevinolin-related compounds. Large-scale preparation of HMG-CoA reductase inhibitor L-679,336

  摘要：

  A novel synthetic route to a mevinolin-related HMG-CoA reductase inhibitor L-679,336 is described. The key features of the synthesis are a diastereoselective osmium tetraoxide catalyzed dihydroxylation reaction and a highly selective, phosphorus-mediated, pinacol-type rearrangement to give ketone 6. In situ multinuclear NMR experiments were used to gain a detailed understanding of the pinacol step. The above route was used for multikilogram preparation of the title compound. Also described are Lewis acid catalyzed rearrangement reactions of epoxide intermediates 4 and 5, as well as the intramolecular hydrosilylation reaction of deacylated olefinic substrates 17 and 18.

  DOI：

  10.1021/jo00011a022