2-endo-(Hydroxymethyl)-3-exo-((methoxymethoxy)methyl)-5-(phenylsulfenyl)-7-oxabicyclo<2.2.1>hept-5-ene

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-endo-(Hydroxymethyl)-3-exo-((methoxymethoxy)methyl)-5-(phenylsulfenyl)-7-oxabicyclo<2.2.1>hept-5-ene
• 英文别名: [(1R,2R,3R,4S)-3-(methoxymethoxymethyl)-5-phenylsulfanyl-7-oxabicyclo[2.2.1]hept-5-en-2-yl]methanol
• 化学式: C₁₆H₂₀O₄S
• 分子量: 308.398
• InChiKey: DKRQQINOVCCEMK-YXWQFLTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  73.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-endo-(Hydroxymethyl)-3-exo-((methoxymethoxy)methyl)-5-(phenylsulfenyl)-7-oxabicyclo<2.2.1>hept-5-ene 在 四丁基碘化铵 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 21.0h， 生成 2-endo-((Benzyloxy)methyl)-3-exo-((methoxymethoxy)methyl)-5-(phenylsulfonyl)-7-oxabicyclo<2.2.1>hept-5-ene
  参考文献：
  名称：

  Sulfone Directed Alkylative Bridge Cleavage of Oxabicyclic Vinyl Sulfones with Organolithium Reagents

  摘要：

  An efficient regio- and stereocontrolled methodology for the alkylative bridge cleavage of oxabicyclic vinyl sulfones is described. A range of 7-oxabicyclo[2.2.1]heptenyl and 8-oxabicyclo[3.2.1]octenyl sulfones has been found to undergo an overall syn S(N)2' opening when treated with a wide variety of organolithium reagents and lithium aluminum hydride. In this manner, highly functionalized cyclohexenyl and cycloheptenyl sulfones, versatile synthetic intermediates, are now available in high yields. The complete stereoselectivity encountered in the exo conjugate addition may be explained by chelation of the organometallic reagent with the oxygen bridge and steric factors. Furthermore, less-strained substrates allow for complete control of the addition and elimination stages.

  DOI：

  10.1021/jo00093a024
• 作为产物：
  描述：

  9-exo-((Methoxymethoxy)methyl)-2-exo-(phenylsulfenyl)-4,8-dioxatricyclo<4.2.1.0^3,7>nonane 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以80%的产率得到2-endo-(Hydroxymethyl)-3-exo-((methoxymethoxy)methyl)-5-(phenylsulfenyl)-7-oxabicyclo<2.2.1>hept-5-ene
  参考文献：
  名称：

  Sulfone Directed Alkylative Bridge Cleavage of Oxabicyclic Vinyl Sulfones with Organolithium Reagents

  摘要：

  An efficient regio- and stereocontrolled methodology for the alkylative bridge cleavage of oxabicyclic vinyl sulfones is described. A range of 7-oxabicyclo[2.2.1]heptenyl and 8-oxabicyclo[3.2.1]octenyl sulfones has been found to undergo an overall syn S(N)2' opening when treated with a wide variety of organolithium reagents and lithium aluminum hydride. In this manner, highly functionalized cyclohexenyl and cycloheptenyl sulfones, versatile synthetic intermediates, are now available in high yields. The complete stereoselectivity encountered in the exo conjugate addition may be explained by chelation of the organometallic reagent with the oxygen bridge and steric factors. Furthermore, less-strained substrates allow for complete control of the addition and elimination stages.

  DOI：

  10.1021/jo00093a024

文献信息

• Sulfone Directed Alkylative Bridge Cleavage of Oxabicyclic Vinyl Sulfones with Organolithium Reagents
  作者：Odon Arjona、Alfonso de Dios、Roberto Fernandez de la Pradilla、Joaquin Plumet、Alma Viso

  DOI：10.1021/jo00093a024

  日期：1994.7

  An efficient regio- and stereocontrolled methodology for the alkylative bridge cleavage of oxabicyclic vinyl sulfones is described. A range of 7-oxabicyclo[2.2.1]heptenyl and 8-oxabicyclo[3.2.1]octenyl sulfones has been found to undergo an overall syn S(N)2' opening when treated with a wide variety of organolithium reagents and lithium aluminum hydride. In this manner, highly functionalized cyclohexenyl and cycloheptenyl sulfones, versatile synthetic intermediates, are now available in high yields. The complete stereoselectivity encountered in the exo conjugate addition may be explained by chelation of the organometallic reagent with the oxygen bridge and steric factors. Furthermore, less-strained substrates allow for complete control of the addition and elimination stages.