(-)-grandisol | 68225-45-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-grandisol
• 英文别名: Cyclobutaneethanol, 1-methyl-2-(1-methylethenyl)-, (1S,2R)-；2-[(1S,2R)-1-methyl-2-prop-1-en-2-ylcyclobutyl]ethanol
• CAS: 68225-45-6
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: SJKPJXGGNKMRPD-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (1S,2R)-2-isopropenyl-1-methylcyclobutaneacetonitrile 在 lithium aluminium tetrahydride 、 L-酒石酸 、 二异丁基氢化铝 作用下， 反应 5.33h， 生成 (-)-grandisol
  参考文献：
  名称：

  大青松酚对映体信息素的两个对映异构体的新合成

  摘要：

  以（）-3-羟基丁酸乙酯为单一手性来源，合成了Boheman信息素组分Grandisol（2-异丙烯基-1-甲基环丁烷-乙醇）的纯对映体。

  DOI：

  10.1016/s0040-4020(01)86806-x

文献信息

• Enantioselective Intermolecular [2+2] Photocycloaddition Reaction of Cyclic Enones and Its Application in a Synthesis of (−)-Grandisol
  作者：Saner Poplata、Thorsten Bach

  DOI：10.1021/jacs.8b01011

  日期：2018.3.7

  The intermolecular [2+2] photocycloaddition of typical cyclic α,β-unsaturated enones, such as 2-cyclohexenone, with olefins was performed in moderate to good yields (42–82%) and with high enantioselectivity (82%–96% ee). An unusual substitution pattern at the chiral oxazaborolidine-AlBr3 Lewis acid complex that promotes the reaction was found to be crucial for the success of the reaction. The method

  典型的环状 α,β-不饱和烯酮（如 2-环己烯酮）与烯烃的分子间 [2+2] 光环加成以中等至良好的产率（42-82%）和高对映选择性（82%-96% ee ）。发现促进反应的手性恶唑硼烷-AlBr3 路易斯酸络合物的不寻常取代模式对反应的成功至关重要。该方法用于对映选择性合成单萜(-)-格兰地醇，以3-甲基-2-环己烯酮为原料，可分六步完成，总产率为13%。
• Synthesis of the both enantiomers of grandisol, the boll weevil pheromone
  作者：K. Mori

  DOI：10.1016/0040-4020(78)88139-3

  日期：1978.1

  Optically active forms of grandisol (2-isopropenyl-1-methylcyclobutane ethanol, 1 and 1') were synthesized from optically active 5-carboxybicyclo[3.2.0]heptan-2-one (2 and its antipode), obtained by resolving the racemate. The optical purities of the synthetic products were determined by the NMR studies using a chiral shift reagent and shown to be 80%. The [α]D values of our synthetic grandisols were

  旋光性形式的大丁醇（2-异丙烯基-1-甲基环丁烷乙醇，1和1 '）是通过拆分外消旋体而获得的旋光性5-羧基双环[3.2.0]庚烷-2-酮（2及其对映体）合成的。合成产物的光学纯度通过使用手性位移试剂的NMR研究确定，显示为80％。我们的合成大单体的[α] D值为±20°（校正后），与马格纳斯的合成（+）-大三角醇（校正后为+ 18.5°）一致，与自然信息素的报道值（+50±10°）不同）。
• PROCESS FOR PRODUCTION OF POLYSUBSTITUTED CYCLOBUTANES AND POLYSUBSTITUTED CYCLOBUTENES
  申请人：National University Corporation Tohoku Unversity

  公开号：EP1775300A1

  公开（公告）日：2007-04-18

  The prior art required specialized substrates or reaction conditions to be used to manufacture polysubstituted cyclobutane compounds and polysubstituted cyclobutene compounds, and the method had poor generality. The type or quantity of the catalyst or solvent used was also problematic in the industrial manufacture of polysubstituted cyclobutane compounds. The present invention provides a method for manufacturing a polysubstituted cyclobutane compound with high stereoselectivity that has low environmental load (is ecologically advantageous) and is applicable to industrial manufacturing from the standpoint of operation, substrate generality, catalyst, solvent, and efficiency. A polysubstituted cyclobutane, a cyclobutene, and a bicyclo[4.2.0]octane compound can be manufactured efficiently, stereoselectively, and in an ecologically advantageous manner by causing a Brønsted acid to act on a mixture of an enol ether compound or 2-siloxydiene compound with an alkene or alkyne compound in which a carbonyl group is substituted at the 1-position in a non-aqueous solvent or without a solvent.

  先前的技术需要使用专门的基质或反应条件来制造多取代环丁烷化合物和多取代环丁烯化合物，并且该方法的普适性较差。在工业制造多取代环丁烷化合物时，所使用的催化剂或溶剂的类型或数量也存在问题。本发明提供了一种制造具有高立体选择性、低环境负荷（具有生态优势）且适用于工业制造的多取代环丁烷化合物的方法，从操作、基质普适性、催化剂、溶剂和效率等方面考虑。通过使布朗斯特酸作用于烯醚化合物或2-硅氧基二烯化合物与在1位取代了羰基的烯烃或炔烃化合物的混合物中，在无水溶剂或不使用溶剂的情况下，可以有效、立体选择性地、具有生态优势地制造多取代环丁烷化合物、环丁烯和双环[4.2.0]辛烷化合物。
• Highly efficient and diastereoselective approaches to (+)- and (−)-grandisol
  作者：Ramón Alibés、José L. Bourdelande、Josep Font、Teodoro Parella

  DOI：10.1016/0040-4020(95)00958-2

  日期：1996.1

  Two new routes to (+)-grandisol and three new routes to (−)-grandisol are described All of them are highly efficient and diastereoselective The common starting material is an easily available homochiral butenolide

  描述了两种新的（+）-大青醇路线和三种新的（-）-大青醇路线，它们都是高效且非对映选择性的。常见的起始原料是容易获得的同手性丁烯内酯
• Process for Production of Polysubstituted Cyclobutanes and Polysubstituted Cyclobutenes
  申请人：Takasu Kiyosei

  公开号：US20080051598A1

  公开（公告）日：2008-02-28

  The prior art required specialized substrates or reaction conditions to be used to manufacture polysubstituted cyclobutane compounds and polysubstituted cyclobutene compounds, and the method had poor generality. The type or quantity of the catalyst or solvent used was also problematic in the industrial manufacture of polysubstituted cyclobutane compounds. The present invention provides a method for manufacturing a polysubstituted cyclobutane compound with high stereoselectivity that has low environmental load (is ecologically advantageous) and is applicable to industrial manufacturing from the standpoint of operation, substrate generality, catalyst, solvent, and efficiency. A polysubstituted cyclobutane, a cyclobutene, and a bicyclo[4.2.0]octane compound can be manufactured efficiently, stereoselectively, and in an ecologically advantageous manner by causing a Brønsted acid to act on a mixture of an enol ether compound or 2-siloxydiene compound with an alkene or alkyne compound in which a carbonyl group is substituted at the 1-position in a non-aqueous solvent or without a solvent.

  先前的技术要求使用专门的基质或反应条件来制造多取代环丁烷化合物和多取代环丁烯化合物，该方法的普适性较差。在工业生产多取代环丁烷化合物时，所使用的催化剂或溶剂的类型或数量也存在问题。本发明提供了一种制造高立体选择性、环境负荷低（具有生态优势）且从操作、基质普适性、催化剂、溶剂和效率的角度适用于工业生产的多取代环丁烷化合物的方法。通过使Brønsted酸作用于烯醚化合物或2-硅氧基二烯化合物与烯烃或炔烃化合物的混合物，其中在1位取代了羰基基团，可以在非水溶剂或无溶剂的情况下高效、立体选择性地、具有生态优势地制造多取代环丁烷、环丁烯和双环[4.2.0]辛烷化合物。