<3S-(3α,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-carbonitrile | 143970-46-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: <3S-(3α,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-carbonitrile
• 英文别名: [3S-(3α,3aα,5aR,7aα,11aβ,11bα)]-(+)-1,3,3a,6,7,7a,8,9,10,11,11a,11b-Dodecahydro-8,8,11a-trimethyl-2H-cyclobuta[j]phenanthrene-3-carbonitrile；(1R,4S,9S,10R,13S,14R)-5,5,9-trimethyltetracyclo[8.6.0.01,14.04,9]hexadec-15-ene-13-carbonitrile
• CAS: 143970-46-1
• 化学式: C₂₀H₂₉N
• 分子量: 283.457
• InChiKey: DLPNOOCWDPKCRP-UQZPWQSVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  <3S-(3α,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-carbonitrile 在 氢氧化钾 、 二甲基硫 、 臭氧 作用下， 以 various solvent(s) 为溶剂， 反应 24.03h， 生成 7H,10H-呋喃并[2,3,4-cd]萘并[2,1-e]异苯并呋喃-7-酮,十四氢-10-羟基-1,1,4a-三甲基-,(4aS,4bR,6aR,8aR,10R,10aS,10bR,12aS)-(9CI)
  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 在 potassium tert-butylate 作用下， 以 乙二醇二甲醚 、 丙酮 、 叔丁醇 为溶剂， 反应 8.25h， 生成 <3S-(3α,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-carbonitrile
  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

文献信息

• 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.
• Spongian pentacyclic diterpenes. Stereoselective synthesis of (-)-dendrillol-1
  作者：Antonio Abad、Manuel Arno、Ana C. Cunat、M. Luisa Marin、Ramon J. Zaragoza

  DOI：10.1021/jo00051a035

  日期：1992.12

  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.