(1S,4R)-1-<(Z)-2-(p-Methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanone | 152898-45-8

• 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: (1S,4R)-1-<(Z)-2-(p-Methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanone
• 英文别名: (1S,4R)-1-[(Z)-2-(p-methoxyphenoxy)vinyl]-7,7-dimethyl-2-norbornanone；(1S,4R)-1-[(Z)-2-(4-methoxyphenoxy)ethenyl]-7,7-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 152898-45-8
• 化学式: C₁₈H₂₂O₃
• 分子量: 286.371
• InChiKey: NMWMILSLUVNQFN-RFTYDGQSSA-N

物化性质

• 沸点：
  397.6±27.0 °C(predicted)
• 密度：
  1.161±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,4R)-1-<(Z)-2-(p-Methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanone 在 18-冠醚-6 cerium(III) chloride 、 叔丁基锂 、 乙烯基-锂 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 、 正戊烷 为溶剂， 反应 2.83h， 生成 (1R,4aR,7R,10E,12R,12aR)-1-(Benzyloxy)-2,3,4,4a,6,7,8,9,12,12a-decahydro-12-(p-methoxyphenoxy)-13,13-dimethyl-7,10-methanobenzocyclodecen-5(1H)-one
  参考文献：
  名称：

  A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol

  摘要：

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.

  DOI：

  10.1021/jo00076a058
• 作为产物：
  描述：

  (+)-7,7-dimethyl-1-vinyl-2-norbornanone 在 正丁基锂 、 二甲基硫 、 臭氧 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.17h， 生成 (1S,4R)-1-<(Z)-2-(p-Methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanone
  参考文献：
  名称：

  A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol

  摘要：

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.

  DOI：

  10.1021/jo00076a058

文献信息

• High-Rate Accelerations in Oxy-Cope Rearrangements Induced by Sulfur Substitution:  Kinetic Study Involving Electronically and Geometrically Differentiated 1-Alkenyl-2-(<i>Z</i>-1-propenyl)-7,7-dimethyl-<i>exo</i>-norbornan-2-ols
  作者：Leo A. Paquette、Y. Ravindra Reddy、Grigoriy Vayner、K. N. Houk

  DOI：10.1021/ja0025402

  日期：2000.11.1

  carbon of the bridgehead vinyl group and the geometric nature of the olefinic center. The results convincingly establish that although an OPMP substituent exerts, at best, a very modest decelerative kinetic effect, the presence of the PhS substituent causes rearrangement to occur approximately 103 times faster by lowering the activation energy to the extent of 3−4 kcal/mol. This remarkable divergence

  已经确定了五种结构相关的外降冰片醇的阴离子促进的氧-科普重排率。这些底物的取代模式的一个关键区别是桥头乙烯基末端碳上是否存在氧或硫官能团以及烯烃中心的几何性质。结果令人信服地证明，尽管 OPMP 取代基最多发挥非常温和的减速动力学效应，但 PhS 取代基的存在通过将活化能降低至 3-4 kcal/mol 的程度，使重排发生速度提高约 103 倍. 这种显着的行为差异被证明与计算预测的过渡态的高度解离性质密切相关。
• Stereocontrolled Oxygenation of Camphor Derivatives as a Prelude to the Complete .beta.-Ring Functionalization of Potential Precursors to Taxol and Structural Analogs Thereof
  作者：Steven W. Elmore、Leo A. Paquette

  DOI：10.1021/jo00109a020

  日期：1995.2

  The possibility of realizing the predominant exo a-hydroxylation of camphor-related ketones is described. Both the direct oxidation of enolate anions with 1-phenyl-N-(phenylsulfonyl)oxaziridine or exposure of the derived silyl enol ethers to dimethyl dioxirane are conducive to exo attack. Following conversion to MOM derivatives, the acidity of the alpha-carbonyl proton is reduced sufficiently to allow direct condensation of these hindered ketones with cyclohexenyllithium reagents. The subsequent anionic oxy-Cope rearrangement of the resulting exo carbinols results in direct conversion to tricyclic products that feature the characteristic C-2,C-9,C-10 B-ring oxygenation pattern resident in taxol. Further, the stereogenic centers are introduced in their proper absolute configuration. The steric demands of the [3,3] sigmatropic shift are discussed and the stereochemical features conducive to the minimization of steric compression subjected to experimental verification.
• A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol
  作者：Leo A. Paquette、Scot K. Huber、Richard C. Thompson

  DOI：10.1021/jo00076a058

  日期：1993.11

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.