meso-(3R,5s,7S)-5-(benzyloxy)-3,7-bis((tert-butyldiphenylsilyl)oxy)cyclohept-1-ene | 217025-88-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: meso-(3R,5s,7S)-5-(benzyloxy)-3,7-bis((tert-butyldiphenylsilyl)oxy)cyclohept-1-ene
• CAS: 217025-88-2
• 化学式: C₄₆H₅₄O₃Si₂
• 分子量: 711.104
• InChiKey: UTMOAQPLKNOYOO-JVIUHAFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.81
• 重原子数：
  51.0
• 可旋转键数：
  11.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  meso-(3R,5s,7S)-5-(benzyloxy)-3,7-bis((tert-butyldiphenylsilyl)oxy)cyclohept-1-ene 在 四氧化锇 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 反应 30.0h， 生成 meso-(1R,2S,3S,5s,7R)-5-(benzyloxy)-3,7-bis((tert-butyldiphenylsilyl)oxy)cycloheptane-1,2-diol 、 meso-(1R,2S,3R,5s,7S)-5-(benzyloxy)-3,7-bis((tert-butyldiphenylsilyl)oxy)cycloheptane-1,2-diol
  参考文献：
  名称：

  Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner−Wadsworth−Emmons Reactions with meso-Dialdehydes

  摘要：

  Results from asymmetric Horner-Wadsworth-Emmons reactions between chiral phosphsnate reagents 3a-d, which contain (1R,2S,5R)-8-phenylmenthol as a chiral auxiliary, and meso-dialdehydes 6 and 14 are presented. It was found that both the geometric selectivities and the levels of asymmetric induction depended on the structure of the phosphonate (i.e., the alkyl group R-1 in the phosphoryl unit) and to a certain extent also on the reaction conditions. Furthermore, the nature of the protecting group used on the a-oxygen substituent in dialdehydes 14 influenced the outcome somewhat. By an appropriate choice of reagent and conditions, either (E)- or (Z)-monoaddition products could be obtained geometrically pure and with good to excellent diastereoselectivities, in synthetically useful yields. Analyses of the absolute configurations of the products showed that the (E)-selective reagents (3a-c) and the (Z)-selective phosphonate 3d reacted at opposite enantiotopic carbonyl groups in the substrates. A mechanistic model which accounts for the products formed is presented.

  DOI：

  10.1021/jo981102z
• 作为产物：
  描述：

  meso-(3R,5s,7S)-5-(benzyloxy)-3,7-diacetoxycyclohept-1-ene 在 咪唑 、 氢氧化钾 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.5h， 生成 meso-(3R,5s,7S)-5-(benzyloxy)-3,7-bis((tert-butyldiphenylsilyl)oxy)cyclohept-1-ene
  参考文献：
  名称：

  Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner−Wadsworth−Emmons Reactions with meso-Dialdehydes

  摘要：

  Results from asymmetric Horner-Wadsworth-Emmons reactions between chiral phosphsnate reagents 3a-d, which contain (1R,2S,5R)-8-phenylmenthol as a chiral auxiliary, and meso-dialdehydes 6 and 14 are presented. It was found that both the geometric selectivities and the levels of asymmetric induction depended on the structure of the phosphonate (i.e., the alkyl group R-1 in the phosphoryl unit) and to a certain extent also on the reaction conditions. Furthermore, the nature of the protecting group used on the a-oxygen substituent in dialdehydes 14 influenced the outcome somewhat. By an appropriate choice of reagent and conditions, either (E)- or (Z)-monoaddition products could be obtained geometrically pure and with good to excellent diastereoselectivities, in synthetically useful yields. Analyses of the absolute configurations of the products showed that the (E)-selective reagents (3a-c) and the (Z)-selective phosphonate 3d reacted at opposite enantiotopic carbonyl groups in the substrates. A mechanistic model which accounts for the products formed is presented.

  DOI：

  10.1021/jo981102z