cis-exo-1,2,4-trimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one | 100351-18-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: cis-exo-1,2,4-trimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one
• 英文别名: (1S,2S,4R,5R)-1,2,4-trimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one
• CAS: 100351-18-6
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: FDRSFUPXOBDUMX-DQUBFYRCSA-N

物化性质

• 沸点：
  233.5±40.0 °C(Predicted)
• 密度：
  1.048±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基呋喃 、 2,4-二溴-3-戊酮 在 cerium(III) chloride 、 tin(ll) chloride 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到cis-exo-1,2,4-trimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one
  参考文献：
  名称：

  镧系元素(III) 三氯化物-氯化锡(II) 介导的α,α'-二溴酮与1,3-二烯或烯胺的环加成反应

  摘要：

  α,α'-二溴酮与 1,3-二烯在 CeCl3-SnCl2 存在下在四氢呋喃中的反应被发现在温和条件下以相当到良好的产率得到相应的 [3+4] 环加合物。呋喃和环戊二烯作为氧烯丙基中间体的高效受体，产生双环环加合物。2,4-二溴-3-戊酮与异戊二烯反应生成[3+4] 和[3+2] 环加合物。[3+2] 环加成与烯胺类似，在用 3% NaOH 乙醇溶液处理后得到 2-环戊烯-1-酮。

  DOI：

  10.1246/bcsj.62.2348

文献信息

• Study of<i>cis/trans</i>and<i>endo/exo</i>Diastereoselectivity in the [4+3]-Cycloaddition Reaction of 2-Functionalized Furans and Dimethyloxyallyl Cation: Preparation of Versatile Cycloheptane Synthons
  作者：Angel M. Montaña、Sandra Ribes、Pedro M. Grima、Francisca García

  DOI：10.1246/cl.1997.847

  日期：1997.9

  A study on the influence of steric and electronic effects of a function attached at C-2 of furans in the yield and diastereoselectivity of [4+3] cycloaddition reactions with oxyallyl cations is presented. In almost all studied furans a cis diastereospecificity and a high endo diastereoselectivity is observed. Increasing bulkyness of the function attached at C-2 of furans, increases the endo diastereoselectivity, but decreases yield. Increasing the electronic density of the furan system, by an electron donating group attached at C-2, increases yield and diastereoselectivity.

  本文研究了呋喃的 C-2 上所附函数的立体效应和电子效应对与氧烯丙基阳离子发生 [4+3] 环加成反应的产率和非对映选择性的影响。在几乎所有研究的呋喃中，都观察到了顺式非对映专一性和高度非对映选择性。增加呋喃 C-2 上所附官能团的体积可提高内向非对映选择性，但会降低产率。通过在 C-2 上连接一个电子供体来增加呋喃体系的电子密度，可以提高产率和非对映选择性。
• Complete assignment of1H and13C NMR data and establishment of the relative stereochemistry of C-1-functionalized 2,4-dimethyl-8-oxabicyclo[3.2.1] oct-6-en-3-one derivatives
  作者：Angel M. Montaña、Pedro M. Grima、Francisca García

  DOI：10.1002/(sici)1097-458x(199907)37:7<507::aid-mrc488>3.0.co;2-b

  日期：1999.7

  The total assignment of the 1H and 13C NMR spectra of 24 cis‐endo and 15 cis‐exo diastereoisomers of C‐1‐substituted 2,4‐dimethyl‐8‐oxabicyclo[3.2.1]oct‐6‐en‐3‐one derivatives was deduced from the concerted application of DEPT, COSY, HETCOR, HMBC, HMQC and PS‐NOESY experiments. The relative stereochemistry of major (cis‐endo) and minor (cis‐exo) diastereoisomers was established on the basis of correlation

  C-1取代的2,4-二甲基-8-氧杂双环[3.2.1]oct-6-en-3-one的24个顺-内和15个顺-外非对映异构体的1H和13C NMR谱的总归属衍生物是从 DEPT、COSY、HETCOR、HMBC、HMQC 和 PS-NOESY 实验的协同应用中推导出来的。主要（顺-内）和次要（顺-外）非对映异构体的相对立体化学是基于它们的 1H 和 13C NMR 数据的相关性研究建立的。版权所有 © 1999 John Wiley & Sons, Ltd.
• Fluoride anion induced novel reaction of α-(sulfonio)ketone triflate
  作者：Yoshihiko Ito、Eiji Nakajo、Katsuhiko Shō、Kohei Tamao

  DOI：10.1016/s0040-4039(00)96092-1

  日期：1987.1

  α-(Phenylmethylsulfonio)ketone triflates (1) are treated with a suspension of KF in aprotic polar solvent to give dimeric 2-acylcyclobutanones (2), which are rearranged to γ,δ-unsaturated δ-valerolactones (3) by acid catalyst.

  用KF在非质子极性溶剂中的悬浮液处理α-（苯基甲基磺基）酮三氟甲磺酸酯（1），得到二聚2-酰基环丁酮（2），通过酸催化剂将其重新排列为γ，δ-不饱和δ-戊内酯（3）。
• Foehlisch, Baldur; Gehrlach, Eberhard; Stezowski, John J., Chemische Berichte, 1986, vol. 119, # 5, p. 1661 - 1682
  作者：Foehlisch, Baldur、Gehrlach, Eberhard、Stezowski, John J.、Kollat, Petra、Martin, Eveline、Gottstein, Wolfgang

  DOI：——

  日期：——
• alpha-Hetero-substituted Furans as Dienes in [4+3] Cycloadditions with 1,3-Dimethyloxyallyl Cation for the Preparation of New Versatile Cycloheptane Synthons: A Study of the Factors Controlling the Diastereoselectivity.
  作者：Angel M. Montaña、Sandra Ribes、Pedro M. Grima、Francisca Garcia、Louisa Barré、Ole Hammerich、Inger Søtofte、Bengt Långström

  DOI：10.3891/acta.chem.scand.52-0453

  日期：——

  [4+3] Cycloaddition reactions of 2-functionalized furans with 1,3-dimethyloxyallyl cation, afford versatile polyfunctionalized cycloheptane synthons. Increasing electron-donating properties and/or decreasing size of the substituent at C-2 of furan improves yield but decreases stereoselectivity. The opposite effect is also observed, so, by designing a bulky enough alpha-substituent it is possible to obtain endo stereospecificity. cis Stereospecificity is observed in all studied cases and it is probably determined by the type of reaction mechanism.