(1R)-(-)-3,3-dimethyl-1-vinyl-2-norbornanone | 123026-58-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R)-(-)-3,3-dimethyl-1-vinyl-2-norbornanone
• 英文别名: (1R,4S)-1-ethenyl-3,3-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 123026-58-4
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: VXFFYPLGXMAHDT-GZMMTYOYSA-N

物化性质

• 沸点：
  212.3±19.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R)-(-)-3,3-dimethyl-1-vinyl-2-norbornanone 在 叔丁基锂 、 双(三甲基硅烷基)氨基钾 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 96.5h， 生成
  参考文献：
  名称：

  Paquette, Leo A.; Teleha, Christopher A.; Taylor, Richard T., Journal of the American Chemical Society, 1990, vol. 112, # 1, p. 265 - 277

  摘要：

  DOI：
• 作为产物：
  描述：

  (1R)-10-(N,N-dimethylaminomethyl)fenchone N-oxide 以 二甲基亚砜 为溶剂， 反应 4.0h， 以75%的产率得到(1R)-(-)-3,3-dimethyl-1-vinyl-2-norbornanone
  参考文献：
  名称：

  A new enantiospecific synthetic procedure to the taxoid-intermediate 10-methylenecamphor, and 10-methylenefenchone

  摘要：

  DOI：

  10.1016/s0957-4166(02)00049-6

文献信息

• Direct oxygenation of enolates generated by anionic oxy-Cope rearrangement. Expedient preparation of polycyclic .alpha.-hydroxy ketones
  作者：Leo A. Paquette、Donald T. DeRussy、Neil A. Pegg、Richard T. Taylor、Thomas M. Zydowsky

  DOI：10.1021/jo00280a023

  日期：1989.9
• Regio- and stereochemical course of the ring expansion of bridged bicyclic ketones to spirocyclic .alpha.-keto tetrahydrofurans.
  作者：Leo A. Paquette、John F. P. Andrews、Corinne Vanucci、David E. Lawhorn、Joanna T. Negri、Robin D. Rogers

  DOI：10.1021/jo00040a042

  日期：1992.7

  The regio- and stereochemical aspects of oxonium-promoted pinacol-like rearrangements have been investigated starting from the bridged bicyclic ketones (+/-)-norcamphor, (1R)-(-)-fenchone, and (1R)-(-)-3,3-dimethyl-1-vinyl-2-norbornanone. 1,2-Addition of 5-lithio-2,3-dihydrofuran to these substrates provided alcohols that smoothly underwent acid-catalyzed ring expansion. Whereas bridgehead carbon migration was observed in the first and third examples, the alternative available 1,2 Wagner-Meerwein shift operated in the fenchone series. In every instance, a substantial kinetic preference for formation of the O-exo spirotetrahydrofuranyl ketone was noted. Positioning of the dihydrofuranyl unit in sterically congested endo environments as accomplished by condensation of the alpha-lithio vinyl ether with (1R)-(+)-camphor, (1S)-(+)-7,7-dimethyl-1-vinyl-2-norbornanone, and (1s)-(-)-apocamphor was accompanied by increased hydrolytic sensitivity. Second-stage ring expansion of two of the spirocyclic ketones was characterized by continued adherence to anticipated migratory aptitudes. However, loss of stereochemistry occurred both at the original alpha-carbon and at the newly introduced stereogenic center. These observations and relevant control experiments are most consistent with a push-pull fragmentation scheme leading to a ring-opened oxonium ion-enol pair that, because they are tethered, find it possible to cyclize. Prior to final bonding, either terminus may rotate relative to the other. The kinetic and thermodynamic interrelationships of these phenomena are discussed.
• Paquette, Leo A.; DeRussy, Donald T.; Vandenheste, Thierry, Journal of the American Chemical Society, 1990, vol. 112, # 14, p. 5562 - 5573
  作者：Paquette, Leo A.、DeRussy, Donald T.、Vandenheste, Thierry、Rogers, Robin D.

  DOI：——

  日期：——
• PAQUETTE, LEO A.;DERUSSY, DONALD T.;VANDENHESTE, THIERRY;ROGERS, ROBIN D., J. AMER. CHEM. SOC., 112,(1990) N4, C. 5562-5573
  作者：PAQUETTE, LEO A.、DERUSSY, DONALD T.、VANDENHESTE, THIERRY、ROGERS, ROBIN D.

  DOI：——

  日期：——