2-endo-benzyloxy-2-exo-methyl-7-oxabicyclo<2.2.1>hept-5-ene | 127716-92-1

• 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: 2-endo-benzyloxy-2-exo-methyl-7-oxabicyclo<2.2.1>hept-5-ene
• 英文别名: 2-endo-benzyloxy-2-exo-methyl-7-oxabicyclo[2.2.1]hept-5-ene；Cqgzuuxzvfcaep-bfhyxjousa-；(1R,4R,5R)-5-methyl-5-phenylmethoxy-7-oxabicyclo[2.2.1]hept-2-ene
• CAS: 127716-92-1；133147-31-6
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: CQGZUUXZVFCAEP-BFHYXJOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-endo-benzyloxy-2-exo-methyl-7-oxabicyclo<2.2.1>hept-5-ene 在 potassium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 (1S,4R,6R)-2-(benzenesulfonyl)-6-methyl-6-phenylmethoxy-7-oxabicyclo[2.2.1]hept-2-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：

  7-oxabicyclo[2.2.1]hept-5-en-2-one 在 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.0h， 生成 2-endo-benzyloxy-2-exo-methyl-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

• Ring-opening Sn2' reactions of 7-oxanorbornenes by organolithium reagents. Regio- and stereospecific synthesis of substituted cyclohexenediols
  作者：Odón Arjona、Roberto Fernández de la Pradilla、Angel Martin-Domenech、Joaquin Plumet

  DOI：10.1016/s0040-4020(01)81475-7

  日期：——

  The nucleophilic Sn2' bridge opening of 7-oxabicyclo[2.2.1] hept-5-en-2-ols with organolithium reagents occurs in a regio- and stereospecific fashion to produce 6-substituted-cyclohex-4-en-1,3-diols, regardless of the stereochemistry at C-2. A free alcohol functionality is necessary to attain complete regiocontrol of the process. The methodology is utilized to prepare an optically pure cyclohexene

  7-氧杂双环[2.2.1]庚-5-烯-2-醇与有机锂试剂的亲核Sn2'桥开口以区域和立体特异性方式发生，以产生6-取代的环己-4-烯-1,3 -二醇，无论在C-2处的立体化学如何。要完全控制该过程，必须使用游离的醇功能。该方法用于制备光学纯的环己烯衍生物（+）-（1S，3S，6R）-6-正丁基-3-甲基-环己-4-en-1,3-二醇（5b），模型系统。
• Regio- and stereospecific synthesis of substituted cyclohexenediols from 7-oxabicyclo[2.2.1]hept-5-en-2-ols and organolithium reagents
  作者：Odón Arjona、Roberto Fernández de la Pradilla、Ernesto García、Angel Martin-Domenech、Joaquín Plumet

  DOI：10.1016/s0040-4039(01)93916-4

  日期：1989.1

  The bridge opening reactions of 7-oxabicyclo[2.2.1]hept-5-en-2-ols,4 and6 with organolithium reagents proceed with complete regio- and stereoselectivity to produce highly functionalized cyclohexene derivatives5 and7, respectively.

  7-氧杂双环[2.2.1]庚-5-烯-2-醇，4和6与有机锂试剂的桥开反应以完全的区域选择性和立体选择性进行，分别产生高度官能化的环己烯衍生物5和7。
• ARJONA, ODON;DE, LA PRADILLA ROBERTO FERNANDEZ, TETRAHEDRON LETT., 30,(1989) N6, C. 6437-6440
  作者：ARJONA, ODON、DE, LA PRADILLA ROBERTO FERNANDEZ

  DOI：——

  日期：——
• 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.