(2S,3aS,4aS,5R,8S,8aR)-2-(hydroxymethyl)-2,5,10,10-tetramethyl-5,8-methanooctahydro-2H-isoxazolo[3,2-b]benzoxazole | 211316-04-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (2S,3aS,4aS,5R,8S,8aR)-2-(hydroxymethyl)-2,5,10,10-tetramethyl-5,8-methanooctahydro-2H-isoxazolo[3,2-b]benzoxazole
• 英文别名: [(1S,2R,5S,7S,9S,10R)-5,10,13,13-tetramethyl-4,8-dioxa-3-azatetracyclo[8.2.1.02,9.03,7]tridecan-5-yl]methanol
• CAS: 211316-04-0
• 化学式: C₁₅H₂₅NO₃
• 分子量: 267.368
• InChiKey: BBPJRQARGRQCII-GFCMYALRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  41.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3aS,4aS,5R,8S,8aR)-2-(hydroxymethyl)-2,5,10,10-tetramethyl-5,8-methanooctahydro-2H-isoxazolo[3,2-b]benzoxazole 在 盐酸 、 四丁基碘化铵 、 sodium hydride 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 8.17h， 生成 (E,6S)-6-hydroxy-6-methyl-7-phenylmethoxyhept-3-en-2-one
  参考文献：
  名称：

  [3 + 2] Cycloadditions between α,β-Unsaturated Esters or Nitroalkenes and Camphor-Derived Oxazoline N-Oxides:  Experimental and Theoretical Study

  摘要：

  Oxazoline N-oxide 2 in the presence of alpha,beta-unsaturated esters or nitroalkenes afforded the corresponding adducts with excellent regio- and stereoselectivities depending of the substitution pattern on the dipolarophile. Especially, inversion of regioselectivity was observed by switching from a 1,2-disubstituted to a 1,1-disubstituted alpha,beta-unsaturated ester. This was not observed when nitroalkenes are used as dipolarophiles. An attempt to rationalize the observed selectivities by semiempirical calculations at RHF AM1 level is described. The cycloadduct 5e has been used as the starting material in a total synthesis of the pheromone (-)-frontalin 12.

  DOI：

  10.1021/jo980326e
• 作为产物：
  描述：

  (2S,3aS,4aS,5R,8S,8aR)-2,5,10,10-tetramethyl-5,8-methanooctahydro-2H-isoxazolo[3,2-b]benzoxazole-2-carboxylic acid methyl ester 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以93%的产率得到(2S,3aS,4aS,5R,8S,8aR)-2-(hydroxymethyl)-2,5,10,10-tetramethyl-5,8-methanooctahydro-2H-isoxazolo[3,2-b]benzoxazole
  参考文献：
  名称：

  [3 + 2] Cycloadditions between α,β-Unsaturated Esters or Nitroalkenes and Camphor-Derived Oxazoline N-Oxides:  Experimental and Theoretical Study

  摘要：

  Oxazoline N-oxide 2 in the presence of alpha,beta-unsaturated esters or nitroalkenes afforded the corresponding adducts with excellent regio- and stereoselectivities depending of the substitution pattern on the dipolarophile. Especially, inversion of regioselectivity was observed by switching from a 1,2-disubstituted to a 1,1-disubstituted alpha,beta-unsaturated ester. This was not observed when nitroalkenes are used as dipolarophiles. An attempt to rationalize the observed selectivities by semiempirical calculations at RHF AM1 level is described. The cycloadduct 5e has been used as the starting material in a total synthesis of the pheromone (-)-frontalin 12.

  DOI：

  10.1021/jo980326e

文献信息

• [3 + 2] Cycloadditions between α,β-Unsaturated Esters or Nitroalkenes and Camphor-Derived Oxazoline <i>N</i>-Oxides:  Experimental and Theoretical Study
  作者：Cyrille Kouklovsky、Olivier Dirat、Thierry Berranger、Yves Langlois、Marie Elise Tran-Huu-Dau、Claude Riche

  DOI：10.1021/jo980326e

  日期：1998.7.1

  Oxazoline N-oxide 2 in the presence of alpha,beta-unsaturated esters or nitroalkenes afforded the corresponding adducts with excellent regio- and stereoselectivities depending of the substitution pattern on the dipolarophile. Especially, inversion of regioselectivity was observed by switching from a 1,2-disubstituted to a 1,1-disubstituted alpha,beta-unsaturated ester. This was not observed when nitroalkenes are used as dipolarophiles. An attempt to rationalize the observed selectivities by semiempirical calculations at RHF AM1 level is described. The cycloadduct 5e has been used as the starting material in a total synthesis of the pheromone (-)-frontalin 12.