(1S,4S,5R,8S,9S,10S)-10-Methyl-1-triisopropylsilanyloxy-11-oxa-tricyclo[6.2.1.0^4,9]undec-6-en-5-ol | 796850-90-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉类
• 英文名称: (1S,4S,5R,8S,9S,10S)-10-Methyl-1-triisopropylsilanyloxy-11-oxa-tricyclo[6.2.1.0^4,9]undec-6-en-5-ol
• CAS: 796850-90-3
• 化学式: C₂₀H₃₆O₃Si
• 分子量: 352.59
• InChiKey: VSYGRGKHQXGMOE-BIEDPOGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  甲氧基-三氟甲基苯 、 (1S,4S,5R,8S,9S,10S)-10-Methyl-1-triisopropylsilanyloxy-11-oxa-tricyclo[6.2.1.0^4,9]undec-6-en-5-ol 在 4-二甲氨基吡啶 作用下， 以 苯 为溶剂， 反应 0.5h， 生成 (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (1S,4S,5R,8S,9S,10S)-10-methyl-1-triisopropylsilanyloxy-11-oxa-tricyclo[6.2.1.0^4,9]undec-6-en-5-yl ester 、 (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (1R,4R,5S,8R,9R,10R)-10-methyl-1-triisopropylsilanyloxy-11-oxa-tricyclo[6.2.1.0^4,9]undec-6-en-5-yl ester
  参考文献：
  名称：

  Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways

  摘要：

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).

  DOI：

  10.1021/ja046154m
• 作为产物：
  描述：

  3-triisopropylsiloxy-1,3-pentadiene 在 sodium tetrahydroborate 、 cerium(III) chloride 、 chiral oxazaborolidinium*Tf₂N^(1-) derivative 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 14.5h， 生成 (1S,4S,5R,8S,9S,10S)-10-Methyl-1-triisopropylsilanyloxy-11-oxa-tricyclo[6.2.1.0^4,9]undec-6-en-5-ol
  参考文献：
  名称：

  Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways

  摘要：

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).

  DOI：

  10.1021/ja046154m