(R)-2,3-Dihydro-2-methyl-2-vinylfuran | 152999-69-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (R)-2,3-Dihydro-2-methyl-2-vinylfuran
• 英文别名: (2R)-2-ethenyl-2-methyl-3H-furan
• CAS: 152999-69-4
• 化学式: C₇H₁₀O
• 分子量: 110.156
• InChiKey: BACHYZGPNOMZNM-ZETCQYMHSA-N

物化性质

• 沸点：
  127.2±40.0 °C(Predicted)
• 密度：
  0.980±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-2,3-Dihydro-2-methyl-2-vinylfuran 在 cerium(III) chloride 、 camphor-10-sulfonic acid 作用下， 反应 0.83h， 生成 (2R,2'R,4'aR,5R,8'aR)-decahydro-2',5,5',5',8'a-pentamethyl-5-vinylspiro-2'-ol
  参考文献：
  名称：

  Stereocontrolled Synthesis of ent-Grindelic Acid. A Useful Example of Diastereofacial Guidance in an Oxonium Ion-Initiated Pinacolic Ring Expansion

  摘要：

  An enantioselective synthesis of (+)-grindelic acid is described, confirming that the dextrorotatory enantiomer is antipodal to the natural diterpenoid. The optically pure bicyclic ketone 5 representing the AB ring system is constructed from the levorotatory Wieland-Miescher ketone and must therefore possess the absolute configuration shown. Coupling of 5 with the 5-lithio derivative of optically active 2,3-dihydrofuran 3 derived from (R)-(-)-linalool was effected for the purpose of realizing acid-catalyzed rearrangement with generation of the appropriate spirocyclic framework. This key step is highly stereocontrolled, leading predominantly to 7. Once the advanced intermediate 15 is available in this fashion, its subsequent exposure to oxidation and dehydration steps led to the target molecule. The synthesis demonstrates unequivocally that natural (-)-grindelic acid is a true labdane diterpenoid.

  DOI：

  10.1021/jo960547p
• 作为产物：
  描述：

  (R)-芳樟醇 在 臭氧 、 三乙胺 作用下， 以 吡啶 、 二氯甲烷 为溶剂， -78.0~180.0 ℃ 、2.67 kPa 条件下， 生成 (R)-2,3-Dihydro-2-methyl-2-vinylfuran
  参考文献：
  名称：

  Enantioselective synthesis of natural (+)-dactyloxene-B and -C by actuation of oxonium ion-initiated pinacol rearrangement

  摘要：

  A direct route is described for assembling the spirocyclic framework of two sesquiterpene ethers derived biogenetically from the cyclization of farnesol with rearrangement of a methyl group.

  DOI：

  10.1016/s0040-4039(00)73835-4

文献信息

• Total synthesis of (+)-grindelic acid by stereocontrolled oxonium ion activated pinacol ring expansion. Chemical proof of the absolute configuration of all grindelane diterpenes
  作者：Leo A. Paquette、Hui-Ling Wang

  DOI：10.1016/0040-4039(95)01187-m

  日期：1995.8

  (+)-Grindelic acid, synthesized enantioselectively from the levorotatory Wieland-Miescher ketone and (-)-linalool and necessarily formulated as 1a, is shown to be antipodal to the major diterpenoid of Grindelia species.

  (+)-Grindelic酸是由左旋Wieland-Miescher酮和（-)-香叶醇对映选择性合成而得，并必须以1a的形式配制，研究表明其对映于Grindelia属主要的倍半萜。
• Oxonium ion-initiated pinacolic ring expansion reactions. Application to the enantioselective synthesis of the spirocyclic sesquiterpene ethers dactyloxene-B and -C
  作者：Marc D. Lord、Joanna T. Negri、Leo A. Paquette

  DOI：10.1021/jo00106a033

  日期：1995.1

  A convergent synthesis of dactyloxene-B (1) and -C (2) from a common optically active intermediate in seven steps has been achieved. Ozonolysis of(R)-(-)-linalool proceeded regioselectively to deliver a lactol, the benzoate of which when thermolyzed gave dihydrofuran 7. The second building block, levorotatory cyclopentanone 8, was produced by kinetically controlled lipase-induced hydrolysis of chloroacetate 15b. Saponification and oxidation of the less reactive ester was sufficient to provide (-)-8 whose condensation with the cerate of 7 gave rise to 19 and set the stage for implementation of the key structural rearrangement step. When stirred with Dowex resin, 19 was isomerized to four ketones. Following chromatographic separation, 20 and 21 were independently transformed into the target molecules via a two-step sequence. The spectral and optical properties of the two dactyloxenes compared very favorably with those reported earlier.
• Single Stereodifferentiation Associated with Carbon Atom Insertion during the Oxonium Ion-Initiated Pinacol Rearrangement of Dihydrofuranyl and Dihydropyranyl Carbinols
  作者：Leo A. Paquette、James C. Lanter、Jeffrey N. Johnston

  DOI：10.1021/jo962019j

  日期：1997.3.1

  The stereoselectivity of the acid-promoted rearrangement of dihydrofuranyl and dihydropyranyl carbinols to spirocyclic ketones has been examined. These kinetically controlled isomerizations result in the ring expansion of the hydroxyl-substituted ring with generation of a newly stereogenic spirocyclic carbon atom. All of the adducts formed from several 4,5-dihydrofurans and cyclobutanone, cyclopentanone, and 2,2-dimethylcyclopentanone proved to be reactive. Of the 5,6-dihydropyrans examined, only the cyclobutanone adducts were sufficiently reactive to warrant study. The product distributions arising from the furanoid systems were characterized by modest discrimination in most cases. The more stereodifferentiating pyranoid systems show product distributions as high as 30:1. These results are explained in terms of transition state geometries (conformationally more flexible in the five-membered examples) while also taking into account the principle of stereoelectronic control.
• Stereocontrolled Synthesis of <i>ent</i>-Grindelic Acid. A Useful Example of Diastereofacial Guidance in an Oxonium Ion-Initiated Pinacolic Ring Expansion
  作者：Leo A. Paquette、Hui-Ling Wang

  DOI：10.1021/jo960547p

  日期：1996.1.1

  An enantioselective synthesis of (+)-grindelic acid is described, confirming that the dextrorotatory enantiomer is antipodal to the natural diterpenoid. The optically pure bicyclic ketone 5 representing the AB ring system is constructed from the levorotatory Wieland-Miescher ketone and must therefore possess the absolute configuration shown. Coupling of 5 with the 5-lithio derivative of optically active 2,3-dihydrofuran 3 derived from (R)-(-)-linalool was effected for the purpose of realizing acid-catalyzed rearrangement with generation of the appropriate spirocyclic framework. This key step is highly stereocontrolled, leading predominantly to 7. Once the advanced intermediate 15 is available in this fashion, its subsequent exposure to oxidation and dehydration steps led to the target molecule. The synthesis demonstrates unequivocally that natural (-)-grindelic acid is a true labdane diterpenoid.
• Enantioselective synthesis of natural (+)-dactyloxene-B and -C by actuation of oxonium ion-initiated pinacol rearrangement
  作者：Leo A. Paquette、Marc D. Lord、Joanna T. Negri

  DOI：10.1016/s0040-4039(00)73835-4

  日期：1993.9

  A direct route is described for assembling the spirocyclic framework of two sesquiterpene ethers derived biogenetically from the cyclization of farnesol with rearrangement of a methyl group.