<3aS-(3aα,5aS,7aα,11aβ,11bα)>-(+)-1,6,7,7a,8,9,10,11,11a,11b-Decahydro-8,8,11a-trimethyl-2H-cyclobutaphenanthren-3(3aH)-one | 57710-52-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <3aS-(3aα,5aS,7aα,11aβ,11bα)>-(+)-1,6,7,7a,8,9,10,11,11a,11b-Decahydro-8,8,11a-trimethyl-2H-cyclobutaphenanthren-3(3aH)-one
• 英文别名: [3aS-(3aα,5aS,7aα,11aβ,11bα)]-(+)-1,6,7,7a,8,9,10,11,11a,11b-Decahydro-8,8,11a-trimethyl-2H-cyclobuta[j]phenanthren-3(3aH)-one；(1S,4S,9S,10R,14S)-5,5,9-trimethyltetracyclo[8.6.0.01,14.04,9]hexadec-15-en-13-one
• CAS: 57710-52-8
• 化学式: C₁₉H₂₈O
• 分子量: 272.431
• InChiKey: ZWHQUJCUUFDEGC-AYTJEOJGSA-N

物化性质

• 熔点：
  76-77 °C
• 沸点：
  371.7±11.0 °C(predicted)
• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 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：

  <3aS-(3aα,5aS,7aα,11aβ,11bα)>-(+)-1,6,7,7a,8,9,10,11,11a,11b-Decahydro-8,8,11a-trimethyl-2H-cyclobutaphenanthren-3(3aH)-one 在 铂 高氯酸 、 氧气 、 lithium diisopropyl amide 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 22.08h， 生成 <3R-(3β,3aα,5aR,7aα,11aβ,11bα)>-(+)-1,3,3a,6,7,7a,8,9,10,11,11a,11b-Dodecahydro-8,8,11a-trimethyl-2H-cyclobutaphenanthrene-3-carboxylic acid
  参考文献：
  名称：

  Spongian pentacyclic diterpenes. Stereoselective synthesis of (-)-dendrillol-1

  摘要：

  A formal total synthesis of the spongian diterpene (-)-dendrillol-1 (3), through a consice approach that could be used for the synthesis of other pentacyclic spongian diterpenes, is reported. The synthesis is based on the intramolecular acetalization of an acid-dialdehyde 4, which is prepared from (+)-podocarp-8(14)-en-13-one (5) via a sequence of transformations involving (a) introduction of a latent dialdehyde unit on 5 by photochemical reaction with acetylene, (b) reductive carboxylation at C-13 of photoadduct 6 to obtain acid 18, and (c) elaboration of the dialdehyde moiety at C-8 and C-14 of 18 by ozonolysis. Several procedures that have been examined for the reductive carboxylation at C-13 of 6 are described. A simple three-step procedure to effect the conversion of a podocarp-8-en-13-one system into a C-17-functionalized beyerane compound is also reported.

  DOI：

  10.1021/jo00051a035
• 作为产物：
  描述：

  Δ⁸⁽¹⁴⁾-podocarpen-13-one 、 乙炔 以 丙酮 为溶剂， 反应 15.0h， 以62%的产率得到<3aS-(3aα,5aS,7aα,11aβ,11bα)>-(+)-1,6,7,7a,8,9,10,11,11a,11b-Decahydro-8,8,11a-trimethyl-2H-cyclobutaphenanthren-3(3aH)-one
  参考文献：
  名称：

  双环[4.2.0]辛烷体系重排至双环[3.2.1]辛烷体系的机理

  摘要：

  使用迁移键上的选择性氘代，已证明了一种协同机制可将包括双环[4.2.0]辛烷体系的四环离子重排至hibaol。

  DOI：

  10.1016/s0040-4020(01)80919-4

文献信息

• Mechanism of the rearrangement of the bicyclo [4.2.0] octan system to the bicyclo [3.2.1] octan system
  作者：Josette Bastard、Duc Do Khac、Marcel Fetizon、Chantal Prevost、Jean-Claude Beloeil

  DOI：10.1016/s0040-4020(01)80919-4

  日期：1991.1

  A concerted mechanism has been demonstrated for the rearrangement of a tetracyclic ion including a bicyclo [4.2.0] octan system to hibaol, using a selective deuteration on the migrating bond.

  使用迁移键上的选择性氘代，已证明了一种协同机制可将包括双环[4.2.0]辛烷体系的四环离子重排至hibaol。
• Synthesis of spongian diterpenes: (−)-spongian-16-oxo-17-al and (−)-acetyldendrillol-1
  作者：Manuel Arnó、Miguel A González、M.Luisa Marı́n、Ramón J Zaragozá

  DOI：10.1016/s0040-4039(00)02339-x

  日期：2001.2

  An efficient diastereoselective synthesis of the spongian diterpenes (−)-spongian-16-oxo-17-al (1) and (−)-acetyldendrillol-1 (13) is described starting from (+)-podocarp-8(14)-13-one (6) via the ester-dialdehyde 11 as key intermediate. The absolute configuration at C-17 in synthetic compound 13 has conclusively been proved by NOE experiments.

  从（+）-podocarp-8（14）-开始描述了海绵双萜（-）-spongian-16-oxo-17-al（1）和（-）-乙酰基树枝钻1（13）的有效非对映选择性合成。13-一（6）经由酯-二醛11作为关键中间体。合成化合物13中C-17处的绝对构型已通过NOE实验得到了证实。
• Abad, Antonio; Agullo, Consuelo; Arno, Manuel, Journal of the Chemical Society. Perkin transactions I, 1994, # 20, p. 2987 - 2992
  作者：Abad, Antonio、Agullo, Consuelo、Arno, Manuel、Marin, M. Luisa、Zaragoza, Ramon J.

  DOI：——

  日期：——
• Analyzing the uniqueness of the rate constants calculated from complex kinetic systems: A study of the hydrolysis of ciclohexanecarbonitriles
  作者：M. Luisa Mar�n、R. J. Zaragoz�、F. F. P�rez Pla

  DOI：10.1002/(sici)1097-4601(1999)31:9<611::aid-kin3>3.0.co;2-d

  日期：——

  In this article, a novel methodology for the study of complex reaction mechanisms is explored, and applied to the kinetic analysis of the hydrolysis reactions of ciclohexanecarbonitriles. The kinetic data were first analyzed with the help of classic linear techniques. Subsequently, the determination of the rate constants by a non-linear, least-squares (LS) fitting method, followed by a novel eigenvalue-eigenvector analysis of the sensitivity coefficients, permitted us to obtain the maximum possible information from the kinetic data. The non-linear, LS-fitting method, carried out by means of a new version of OPKINE program, allowed the calculation of all the rate constants of the mechanism; in addition, the sensitivity analysis permitted us to establish the uniqueness and reliability of calculated rate coefficients. Finally, the results of the sensitivity analysis were tested by means of a simulation procedure, and the results compared to those obtained from classic linear methods. (C) 1999 John Wiley G Sons, Inc. Int I Chem Kinet 31: 611-626, 1999.
• BASTARD, JOSETTE;DO, KHAC DUC;FETIZON, MARCEL;PREVOST, CHANTAL;SELOEIL, J+, TETRAHEDRON, 47,(1991) N, C. 229-238
  作者：BASTARD, JOSETTE、DO, KHAC DUC、FETIZON, MARCEL、PREVOST, CHANTAL、SELOEIL, J+

  DOI：——

  日期：——