(1R,2S,3R,4S)-(3-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-oxy)ethyne | 157358-08-2

• 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,2S,3R,4S)-(3-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-oxy)ethyne
• 英文别名: (1R,2S,3R,4S)-3-(2,2-dimethylpropoxy)-2-ethynoxy-1,7,7-trimethylbicyclo[2.2.1]heptane
• CAS: 157358-08-2
• 化学式: C₁₇H₂₈O₂
• 分子量: 264.408
• InChiKey: FNWUMVRCKQLNFF-WBOJAVRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S,3R,4S)-(3-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-oxy)ethyne 在 zirconocene hydrochloride 、 对苯二酚 、 copper(l) chloride 作用下， 以 xylene 为溶剂， 反应 8.75h， 生成 (1S,2S,3S,6R)-3,6-bis<(1R,2S,3R,4S)-3-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-oxy>cyclohex-4-en-1,2-dicarbonitrile
  参考文献：
  名称：

  Chiral (E,E)-1,4-dialkoxy-1,3-butadienes. 2. Conformational studies and Diels-Alder reactions with symmetric dienophiles

  摘要：

  The first examples of Diels-Alder reactions of chiral, C-2-symmetric (E,E)-1,4-dialkoxy-1,3-butadienes are described. The cycloadditions with maleic anhydride lead in all instances to the exclusive formation of the endo adducts. C-2h-Symmetric dienophiles such as fumaronitrile and diethyl fumarate react with variable diastereoselectivities; best results are obtained with the camphor-derived diene Id, whose reaction with diethyl fumarate takes place with complete facial selectivity. A theoretical analysis, using the SCF-MO procedure AM1, of the conformations of the dialkoxydienes has been used to rationalize the steric course of the cycloadditions. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00086-1
• 作为产物：
  描述：

  三氯乙烯 、 (1R,2S,3R,4S)-3-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-ol 在 potassium hydride 作用下， 生成 (1R,2S,3R,4S)-(3-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-oxy)ethyne
  参考文献：
  名称：

  A convenient synthesis of hexacarbonyldicobalt complexes of chiral (non-racemic) terminal alkoxyacetylenes

  摘要：

  The hexacarbonyldicobalt complexes of chiral (non-racemic) unsubstituted terminal alkoxyacetylenes have been synthesized for the first time by a novel procedure that involves one-pot transformation of a chiral alcohol to the corresponding trimethylsilylated alkoxy acetylene, followed by complexation and protodesilylation (also one-pot). The synthesis is efficient and amenable to the preparation of multigram quantities.

  DOI：

  10.1016/0022-328x(94)80183-5

文献信息

• Experimental and theoretical studies on the diastereoselective diels-alder reactions of chiral 1-alkoxy-1,3-butadienes. I: Parent system and 4-substituted derivatives
  作者：Marina Virgili、Miquel A Pericàs、Albert Moyano、Antoni Riera

  DOI：10.1016/s0040-4020(97)00854-5

  日期：1997.9

  Chiral 1-alkoxy-1,3-dienes (parent and 4-substituted) have been prepared from the corresponding chiral alkoxyacetylenes in a stereoselective manner following a 2C + 2C approach. The Diels-Alder reactions of the dienes with maleic anhydride and 4-phenyl-3H-1,2,4-triazoline-3,5-dione take place with significant diastereoselectivity. Theoretical calculations on these cycloadditions, performed with the

  按照2C + 2C方法，从相应的手性烷氧基乙炔以立体选择性的方式制备了手性1-烷氧基-1,3-二烯（母体和4-取代的）。二烯与马来酸酐和4-苯基-3 H -1,2,4-三唑啉-3,5-二酮的狄尔斯-阿尔德反应具有非对映选择性。用SCF-MO方法AM1进行的这些环加成反应的理论计算已用于加合物的立体化学分配中。
• Chiral (E,E)-1,4-dialkoxy-1,3-butadienes. 1. Stereoselective synthesis
  作者：Marina Virgili、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1016/s0040-4039(97)01622-5

  日期：1997.9

  A two step, totally stereoselective synthesis of (E,E)-1,4-dialkoxy-1,3-butadienes from chiral secondary alcohols has been developed. The key step involves the regio- and stereoselective hydrozirconation of alkoxyethynes derived from chiral alcohols; the intermediate (E)-(2-alkoxyvinyl)zirconium compounds, after treatment with cuprous chloride and thermally induced decomposition of the corresponding

  已经开发了由手性仲醇进行的两步全立体选择性合成（E，E）-1,4-二烷氧基-1,3-丁二烯的方法。关键步骤涉及衍生自手性醇的烷氧基乙炔的区域和立体选择性加氢锆化反应。中间体（E）-（2-烷氧基乙烯基）锆化合物在用氯化亚铜处理并热诱导分解相应的（2-烷氧基乙烯基）铜后，以中等收率得到二烷氧基丁二烯，但具有完全的（E，E）非对映选择性。
• Chiral auxiliary-induced stereocontrol in intramolecular Pauson-Khand reactions leading to angular triquinanes
  作者：Jordi Tormo、Xavier Verdaguer、Albert Moyano、Miquel A Pericàs、Antoni Riera

  DOI：10.1016/0040-4020(96)00844-7

  日期：1996.10

  thermally induced Pauson-Khand intramolecular cyclization of 1-(3-alkoxy-2-propynyloxy)methylcyclopentenes (2) and 1-(5-alkoxy-4-pentynyl)cyclopentenes (3), derived from chiral secondary alcohols, leads to the tricyclic enones (9) and (10), respectively, in moderate yields and with variable diastereoselectivities. Among the chiral alcohols that we have examined, enynes derived from Oppolzer's 3-(ne

  衍生自手性仲醇的1-（3-烷氧基-2-丙炔氧基）甲基环戊烯（2）和1-（5-烷氧基-4-戊炔基）环戊烯（3）的Pauson-Khand分子内热诱导三环烯酮（9）和（10），分别具有中等收率和非对映选择性。在我们研究的手性醇中，衍生自Oppolzer的3-（新戊氧基）异冰片醇4c的烯炔可提供色谱上可分离的非对映异构体，而衍生自10-（甲硫基）异冰片醇4d的烯属化合物以优异的立体控制环化（高达12：1 dr，这是手性辅助立体控制的分子内Pauson-Khand反应迄今记录的最高值之​​一）。这些结果首次打开了对角三联烷的对映选择性合成的途径，其中三环骨架是从一个单环烯炔以单一步骤立体选择性地构建的，而没有内部立体生成中心。
• Enantioselective Construction of Angular Triquinanes through an Asymmetric Intramolecular Pauson−Khand Reaction. Synthesis of (+)-15-Nor-pentalenene
  作者：Jordi Tormo、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1021/jo9700538

  日期：1997.7.1
• Chiral (E,E)-1,4-dialkoxy-1,3-butadienes. 2. Conformational studies and Diels-Alder reactions with symmetric dienophiles
  作者：Marina Virgili、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1016/s0040-4020(99)00086-1

  日期：1999.3

  The first examples of Diels-Alder reactions of chiral, C-2-symmetric (E,E)-1,4-dialkoxy-1,3-butadienes are described. The cycloadditions with maleic anhydride lead in all instances to the exclusive formation of the endo adducts. C-2h-Symmetric dienophiles such as fumaronitrile and diethyl fumarate react with variable diastereoselectivities; best results are obtained with the camphor-derived diene Id, whose reaction with diethyl fumarate takes place with complete facial selectivity. A theoretical analysis, using the SCF-MO procedure AM1, of the conformations of the dialkoxydienes has been used to rationalize the steric course of the cycloadditions. (C) 1999 Elsevier Science Ltd. All rights reserved.