(+/-)-exo-bicyclo[2.2.1]hept-5-en-2-ylmethyl benzoate | 135560-47-3

• 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: (+/-)-exo-bicyclo[2.2.1]hept-5-en-2-ylmethyl benzoate
• 英文别名: [(1S,2R,4S)-2-bicyclo[2.2.1]hept-5-enyl]methyl benzoate
• CAS: 135560-47-3
• 化学式: C₁₅H₁₆O₂
• 分子量: 228.291
• InChiKey: IVXACWABDOBWNU-YUTCNCBUSA-N

物化性质

• 沸点：
  329.8±11.0 °C(Predicted)
• 密度：
  1.130±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-exo-bicyclo[2.2.1]hept-5-en-2-ylmethyl benzoate 在 potassium permanganate 、 甲基三辛基氯化铵 、 溶剂黄146 作用下， 以 水 、 苯 为溶剂， 反应 23.0h， 以91%的产率得到(+/-)-(1β,3β,4α)-4-benzoyloxymethyl-1,3-cyclopentanedicarboxylic acid
  参考文献：
  名称：

  3'-homo-2'-脱氧-和2'-homo-3'-脱氧-碳环核苷的两种前体的发散合成

  摘要：

  Aminocyclopentanedimethanols 4和5 - ，它们是为2'-脱氧和3'-deoxycarbonucleosides高级同系物的合成兴趣，分别有效地从（±）开始发散途径制备外-二环〔2.2.1〕庚-5-烯-2-甲醛 在关键步骤中，常见中间体（±）-（1β，3β，4α）-4-苯甲酰氧基甲基-1,3-环戊烷二羧酸酐的氨解和随后的酯化反应产生了几乎等摩尔的两种易于分离的异构氨基甲酰基酯。

  DOI：

  10.1016/s0040-4020(02)01053-0
• 作为产物：
  描述：

  exo-2-formylbicyclo[2.2.1]hept-5-ene 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 甲醇 、 水 为溶剂， 反应 73.0h， 生成 (+/-)-exo-bicyclo[2.2.1]hept-5-en-2-ylmethyl benzoate
  参考文献：
  名称：

  3'-homo-2'-脱氧-和2'-homo-3'-脱氧-碳环核苷的两种前体的发散合成

  摘要：

  Aminocyclopentanedimethanols 4和5 - ，它们是为2'-脱氧和3'-deoxycarbonucleosides高级同系物的合成兴趣，分别有效地从（±）开始发散途径制备外-二环〔2.2.1〕庚-5-烯-2-甲醛 在关键步骤中，常见中间体（±）-（1β，3β，4α）-4-苯甲酰氧基甲基-1,3-环戊烷二羧酸酐的氨解和随后的酯化反应产生了几乎等摩尔的两种易于分离的异构氨基甲酰基酯。

  DOI：

  10.1016/s0040-4020(02)01053-0

文献信息

• Synthesis of Novel Carbocyclic Nucleoside Analogues Derived from 2-(Hydroxymethyl)bicyclo[2.2.1]heptane
  作者：Milan Dejmek、Hubert Hřebabecký、Martin Dračínský、Antonín Holý

  DOI：10.1135/cccc20071523

  日期：——

  The key intermediates, [(1R*,2R*,4R*,6R*)-6- (12a) and [(1R*,2R*,4R*,5S*)-5-(hydroxymethyl)- bicyclo[2.2.1]heptan-2-yl]methyl benzoates (12b), were prepared from (1R*,2S*,4R*)- bicyclo[2.2.1]hept-5-en-2-ylmethyl benzoate by hydroboration, oxidation with pyridinium dichromate and subsequent reduction of the thus obtained ketones. The Mitsunobu reaction of12aand12bwith 6-chloropurine afforded 6-chloropurine derivatives, which were converted into others purine analogues. Thymine analogues were prepared from [(1R*,2R*,4S*,6S*)-6- (25a) and [(1R*,2S*,4R*,5S*)-5-aminobicyclo[2.2.1]heptan-2-yl]methanols (25b), which were prepared from alcohols12aand12bin several easy steps.

  关键中间体，[(1R*,2R*,4R*,6R*)-6- (12a) 和 [(1R*,2R*,4R*,5S*)-5-(羟甲基)-双环[2.2.1]庚烷-2-基]甲基苯甲酸酯 (12b)，是从(1R*,2S*,4R*)-双环[2.2.1]庚-5-烯-2-基甲基苯甲酸酯经氢硼化、吡啶二铬酸盐氧化和随后还原所得的酮体制备而成。12a和12b与6-氯嘧啶的三烯甲酚反应得到6-氯嘧啶衍生物，进而转化为其他嘌呤类似物。胸苷类似物是从[(1R*,2R*,4S*,6S*)-6- (25a) 和 [(1R*,2S*,4R*,5S*)-5-氨基双环[2.2.1]庚烷-2-基]甲醇 (25b) 制备而成，这些化合物是从醇类12a和12b经过几个简单步骤制备得到的。
• Asymmetric Diels–Alder reactions of 2-fluoroacrylic acid derivatives. Part 2: A remarkable effect of fluorine substituent on the diastereoselectivity
  作者：Hisanaka Ito、Akio Saito、Takeo Taguchi

  DOI：10.1016/s0957-4166(98)00196-7

  日期：1998.6

  efficient construction of a chiral monofluorinated tertiary carbon was achieved by a highly exo- and diastereofacial selective Diels–Alder reaction of a 2-fluoroacrylic acid derivative derived from 8-phenylmenthol, and cyclopentadiene. The substituent effect of the fluorine on the selectivities is remarkable as compared with the other substituents at the α-position of the acrylate.

  手性一氟化物叔碳的有效的结构是由一个高度实现外从8-苯基薄荷醇，和环戊二烯衍生的2-氟代丙烯酸衍生物的和选择性diastereofacial Diels-Alder反应- 。与丙烯酸酯的α位上的其他取代基相比，氟对选择性的取代效果显着。
• Controlled molecular design of ether- and ester-bridged norbornenes and their ring-opening metathesis polymerizations
  作者：Alaa S Abd-El-Aziz、Andrea L Edel、Leslie J May、Karen M Epp、Harold M Hutton

  DOI：10.1139/v99-164

  日期：1999.11.1

  A series of functionalized polynorbornenes containing pendent ether- or ester-bridged poly(aromatic ether) chains were prepared. The ether-bridged norbornene complex was synthesized via cyclopentadienyliron-mediated nucleophilic aromatic substitution reactions. This methodology, combined with that of dicyclohexylcarbodiimide-mediated coupling, allowed for the formation of novel oligomeric aryl ether and ester substituted norbornene complexes. Photolytic demetallation gave the monomers in good yields. Structural identification of the exo and endo isomers of both the metallated and demetallated norbornene derivatives was accomplished using HH and CH COSY NMR techniques. Ring-opening metathesis polymerization (ROMP) of these monomers using RuCl₃(hydrate) and (Cy₃P)₂Cl₂Ru=CHPh allowed for the preparation of the functionalized polynorbornenes. Thermal analysis of the resulting polymeric materials demonstrated greater thermal stability as the number of aryl ether groups increased.Key words: aromatic ethers, cyclopentadienyliron, polynorbornene, ROMP, ruthenium catalysts.

  一系列含有侧链醚或酯桥联聚芳醚链的功能化聚诺博烯被制备出来。醚桥联诺博烯配合物是通过环戊二烯基铁介导的亲核芳香取代反应合成的。这种方法与二环己基碳二亚胺介导的偶联相结合，允许形成新型的寡聚芳基醚和酯取代诺博烯配合物。光解金属化反应以良好的产率给出单体。使用HH和CH COSY NMR技术对金属化和去金属化诺博烯衍生物的exo和endo异构体进行了结构鉴定。使用RuCl₃(hydrate)和(Cy₃P)₂Cl₂Ru=CHPh进行开环烯烃转化聚合（ROMP）制备功能化聚诺博烯。所得聚合物的热分析表明，随着芳醚基团数的增加，热稳定性更高。关键词：芳香醚，环戊二烯基铁，聚诺博烯，ROMP，钌催化剂。
• Fine-tuned remote control of electrophilic additions to substituted norbornenes
  作者：Odon Arjona、Roberto Fernandez de la Pradilla、Joaquin Plumet、Alma Viso

  DOI：10.1021/jo00021a049

  日期：1991.10
• Divergent synthesis of two precursors of 3′-homo-2′-deoxy- and 2′-homo-3′-deoxy-carbocyclic nucleosides
  作者：José M Blanco、Franco Fernández、Xerardo Garcı́a-Mera、José E Rodrı́guez-Borges

  DOI：10.1016/s0040-4020(02)01053-0

  日期：2002.10

  synthesis of higher homologues of 2′-deoxy- and 3′-deoxycarbonucleosides, respectively, were efficiently prepared by divergent routes starting from (±)-exo-bicyclo[2.2.1]hept-5-ene-2-carbaldehyde. In the key step, ammonolysis of the common intermediate (±)-(1β,3β,4α)-4-benzoyloxymethyl-1,3-cyclopentanedicarboxylic anhydride and subsequent esterification afford near-equimolar amounts of two easily separable

  Aminocyclopentanedimethanols 4和5 - ，它们是为2'-脱氧和3'-deoxycarbonucleosides高级同系物的合成兴趣，分别有效地从（±）开始发散途径制备外-二环〔2.2.1〕庚-5-烯-2-甲醛 在关键步骤中，常见中间体（±）-（1β，3β，4α）-4-苯甲酰氧基甲基-1,3-环戊烷二羧酸酐的氨解和随后的酯化反应产生了几乎等摩尔的两种易于分离的异构氨基甲酰基酯。