endo-cis-7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-diol diacetate | 135505-67-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: endo-cis-7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-diol diacetate
• 英文别名: [(1S,2R,3S,4R)-3-acetyloxy-7-oxabicyclo[2.2.1]hept-5-en-2-yl] acetate
• CAS: 135505-67-8
• 化学式: C₁₀H₁₂O₅
• 分子量: 212.202
• InChiKey: AUOFGMGZPIEXPW-FIRGSJFUSA-N

物化性质

• 熔点：
  81-83 °C
• 沸点：
  280.3±40.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  endo-cis-7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-diol diacetate 在 三氯化硼 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 (1α,2α,3β,6β)-6-chloro-4-cyclohexene-1,2,3-triol triacetate
  参考文献：
  名称：

  由呋喃和碳酸亚乙烯酯的内环加合物合成卤代十二烷糖醇

  摘要：

  描述了一种制备具有conduritol-A结构的卤代conduritols的方法。由呋喃和碳酸亚乙烯酯的Diels-Alder反应制得的内-和外-环加合物衍生物的混合物通过水解（K 2 CO 3 / MeOH）然后乙酰化（Ac 2 O /吡啶）转化为二乙酸酯衍生物。三卤化硼（BBr 3或BCl 3）辅助在-78°C下在CH 2 Cl 2中的内乙酸双乙酸酯的开环，得到（1α，2α，3β，6β）-6-卤代-4-环己烯-1， 2,3-三醇1,2-二乙酸酯，通过乙酰化（AcCl）制备相应的三乙酸酯。反式-三乙酸酯（MeOH / HCl）的酯化得到（1α，2α，3β，6β）-6-卤代-4-环己烯-1，2，3-三醇（X ＝ Br或Cl）。BF 3 -Assisted所述的开环内型-二乙酸根在CH 2氯2，得到（1α，2α，3β，6β）-6-氯-4-环己烯-1,2,3-三醇-1,2-二乙酸酯，借助于卤素交换。

  DOI：

  10.1016/s0040-4020(03)00510-6
• 作为产物：
  描述：

  endo-3,5,10-Trioxatricyclo<5.2.1.0^2,6>dec-8-en-4-on 在 palladium on activated charcoal 盐酸 、 sodium hydroxide 、 氢气 作用下， 以 乙醇 、 水 为溶剂， 生成 endo-cis-7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-diol diacetate
  参考文献：
  名称：

  电子需求增加引起的氧气参与

  摘要：

  Le dibrosylate du cis,endo-oxa-7bicyclo [2.2.1] heptanediol-2,3 s'acetolyse 加快速反应 que 子异构体。Dans la serie monobrosylate 通讯员，l'isomere exo s'acetolyse plus rapidement que l'isomere exo

  DOI：

  10.1021/ja00311a053

文献信息

• A Straightforward Synthesis of 2,3,4,5-Tetrasubstituted Tetrahydrofuran Derivatives
  作者：Joaquín Plumet、Ana Aljarilla

  DOI：10.1055/s-0028-1083180

  日期：——

  A concise synthesis of 2,3,4,5-tetrasubstituted tetrahydrofurans starting from furan via 7-oxabicyclo[2.2.1]hept-5-ene-2,3-diol (2,3-dihydroxy-7-oxanorbomene) derivatives is reported. The key step of these transformations was the sequence ring-opening metathesis-cross metathesis (ROM-CM) reactions of the oxabicyclic compounds in the presence of ethylene and using commercially available 2nd generation

  2,3,4,5-四取代四氢呋喃从呋喃通过 7-oxabicyclo[2.2.1]hept-5-ene-2,3-diol (2,3-dihydroxy-7-oxorobomene) 衍生物的简明合成是报道。这些转化的关键步骤是氧二环化合物在乙烯存在下并使用市售的第二代 Hoveyda-Grubbs 催化剂进行序列开环复分解 - 交叉复分解 (ROM-CM) 反应。
• Stereoselective ring-opening reactions with AcBr and AcCl. A new method for preparation of some haloconduritols
  作者：Arif Baran、Cavit Kazaz、Hasan Seçen

  DOI：10.1016/j.tet.2003.11.054

  日期：2004.1

  A similar reaction of the exo-diacetate with AcBr in the presence of H2SO4 resulted in bromine addition. The formation of bromine from the reaction of AcBr and H2SO4 was observed by independent experiments. H2SO4-catalyzed reaction of endo-cis-7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-diol diacetate with AcX (X=Br, Cl) gave (1α,2α,3β,6β)-6-halo-4-cyclohexene-1,2,3-triol triacetates. The reaction of the transoid-epoxide

  ACX（X为Br，cl）对7-氧杂-二环的动作[2.2.1]庚-5-烯-2,3-二醇二乙酸酯和transoid -epoxide从丙酮化合物制备环己基-3,5-研究了二烯-顺-1,2-二醇。H 2 SO 4催化AcCl裂解exo - cis -7-oxa-双环[2.2.1]庚-5-烯-2,3-二醇二乙酸酯，得到（1α，2α，3α，6β）-6-氯-4-环己烯-1,2,3-三醇三乙酸酯，从中所获得的对应的chloroconduritol反-esterification（甲醇/ HCl）中。H 2 SO 4存在下，exo- diacetate与AcBr的相似反应导致添加溴。通过独立实验观察到由AcBr和H 2 SO 4反应形成的溴。ħ 2 SO 4的反应催化的内切-顺式-7-氧杂-双环[2.2.1]与ACX（X为Br，cl）庚-5-烯-2,3-二醇二乙酸酯，得到（1α，2α，3β ，6β）-6-
• Living ring-opening metathesis polymerization of 2,3-difunctionalized 7-oxanorbornenes and 7-oxanorbornadienes by Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(O-tert-Bu)2 and Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(OCMe2CF3)2
  作者：Guillermo C. Bazan、John H. Oskam、Hyun Nam Cho、Lee Y. Park、Richard R. Schrock

  DOI：10.1021/ja00018a028

  日期：1991.8

  7-Oxabenzonorbornadiene (9), 2,3-endo-cis-diacetoxy-7-oxanorbornene, and 2,3-endo-cis-(isopropylidenedioxy)-7-oxanorbornene can be polymerized by Mo(CHCMe2R)(NAr)(O-t-Bu)2 (Ar = 2,6-C6H3-i-Pr2; R = CH3, C6H5) ([Mo]-(CHCMe2R)) to give polymers with narrow molecular weight distributions (PDI < 1.17). However, 2,3-bis(trifluoromethyl)-7-oxanorbornadiene (1), 2,3-dicarbomethoxy-7-oxanorbornadiene (4), and 2,3-trans-dicyano-7-oxanorborn-5-ene (12) form stable metallacycles upon addition to [Mo](CHCMe2R). The rate of reaction of 1 with [Mo](CHCMe2R) has been determined qualitatively to be comparable to that of norbornene in competition experiments, a result that implies that the lone pair on the oxygen in the 7-position is accelerating metallacycle formation. The metallacycle that results from addition of 1 to [Mo](CHCMe2Ph) is square pyramidal with the imido ligand in the apical position. (Crystal data for 2b: a = 12.420 (3) angstrom, b = 15.466 (4) angstrom, c = 20.856 (6) angstrom, V = 3852 (2) angstrom 3, beta = 105.97 (2)degrees, space group = P2(1)/n, Z = 4, M(r) = 779.76, rho = 1.345 g/cm3, mu = 3.9 cm-1, R1 = 0.049, R2 = 0.068.) The MoC3 ring is planar with the CMe2Ph group pointed toward the imido ligand and the C-7 frame of the monomer pointed away from it (a trans metallacyclic ring). The oxygen in the 7-position of the norbornene moiety is located 3.332 (4) angstrom from the metal. Electronic and steric factors that influence first-order breakup of the metallacycle have been studied for monomers 1 and 4. The more reactive catalyst, Mo(CHCMe2Ph)(NAr)(OCMe2CF3)2, can polymerize 1, 4, and 12 to give polymers with narrow molecular weight distributions (PDI < 1.15).