1-(2-Methyl-1-((trimethylsilyl)methyl)-2-propenyl)cyclohexanol | 133447-98-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(2-Methyl-1-((trimethylsilyl)methyl)-2-propenyl)cyclohexanol
• 英文别名: 1-(2-Methyl-1-trimethylsilylmethyl-2-propenyl)cyclohexanol；1-(3-methyl-1-trimethylsilylbut-3-en-2-yl)cyclohexan-1-ol
• CAS: 133447-98-0
• 化学式: C₁₄H₂₈OSi
• 分子量: 240.461
• InChiKey: NCZHVYNJTLXECK-UHFFFAOYSA-N

物化性质

• 沸点：
  291.0±15.0 °C(Predicted)
• 密度：
  0.900±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.21
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  三甲基氯硅烷 、 环己酮 、 天然橡胶 在 magnesium 作用下， 生成 1-(1-methyl-1-((trimethylsilyl)methyl)-2-propenyl)cyclohexanol 、 1-(2-Methyl-1-((trimethylsilyl)methyl)-2-propenyl)cyclohexanol
  参考文献：
  名称：

  Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles

  摘要：

  Highly reactive magnesium reacts with a wide variety of substituted 1,3-dienes to give the corresponding substituted (2-butene-1,4-diyl)magnesium complexes. Reactions of symmetrical (2-butene-1,4-diyl)magnesium with alpha,omega-alkylene dihalides form three-, four-, five-, and six-membered carbocycles. Significantly, the cyclizations are always stereospecific and completely regioselective. Depending on the initial 1,3-diene and specific electrophiles, uncyclized products can be obtained. Stepwise reactions of (2,3-dimethyl-2-butene-1,4-diyl)magnesium with two different electrophiles afford polyfunctionalized ketones with the generation of a quaternary center. Formal 1,2-additions can be effected in this manner. Substituted five- and six-membered cyclic ketones can also be synthesized in one step by this approach. Treatment of unsymmetrical (2-butene-1,4-diyl)magnesium complexes with triorganosilyl chlorides followed by cyclohexanone results in additions across a terminal double bond with high regioselectivity. Silicon-containing heterocycles or spiro compounds can be readily synthesized by using the bis-Grignard reagents.

  DOI：

  10.1021/jo00009a034

文献信息

• Preparation and use of (2-butene-1,4-diyl)magnesium complexes in organic
  申请人：Board of Regents of the University of Nebraska

  公开号：US05231205A1

  公开（公告）日：1993-07-27

  The magnesium complexes of cyclic hydrocarbons, such as 1,2-dimethylenecycloalkanes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4-diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, or bromoalkylnitriles serve as a convenient method for synthesizing spirocyclic systems. Significantly, spirocarbocycles prepared by this The present invention was made with Government support under Contract No. GM35153 awarded by the National Institute of Health. The Government has certain rights in the invention.

  环烃的镁配合物，比如1,2-二亚甲基环烷烃，可以使用高反应性的镁轻易制备得到高收率。这些(2-丁烯-1,4-二基)镁试剂与电子亲和剂，如二溴代烷、烷基重甲基苯磺酸酯或溴代烷基腈的反应，可作为合成螺环系统的方便方法。值得注意的是，通过这种方法制备的螺环碳环化合物是在由国家卫生研究院授予的GM35153合同支持下完成的。政府对该发明有一定的权利。
• Preparation and use of (2-butene-1,4-diyl) magnesium complexes in
  申请人：Board of Regents of the University of Nebraska

  公开号：US05581004A1

  公开（公告）日：1996-12-03

  The magnesium complexes of cyclic hydrocarbons and conjugated dienes, such as 1,2-dimethylenecycloalkanes and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4-diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.-lactones, including spiro .gamma.-lactones, can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with a ketone or aldehyde and carbon dioxide.

  环烃和共轭二烯的镁配合物，例如1,2-二亚甲基环烷和1,3-丁二烯，可以使用高反应性镁高产率地制备。这些(2-丁烯-1,4-二基)镁试剂与电子亲和剂，如二溴代烷，烷基对甲苯磺酸酯，烷基三氟甲烷磺酸酯，溴代烷基腈，酯或酰胺的反应，可作为合成碳环系统的方便方法。值得注意的是，通过这种方法制备的碳环中含有外环双键或一个环中的酮基等官能团，可用于进一步扩展这些分子。此外，含有取代五元环的融合双环系统可以通过(2-丁烯-1,4-二基)镁配合物与羧酸酯或酸卤反应在高温下方便地制备，而低温则导致β,γ-不饱和酮的区域选择性合成。此外，γ-内酯，包括螺环γ-内酯，可以通过(2-丁烯-1,4-二基)镁配合物与酮或醛以及二氧化碳的反应在一个反应中轻松制备。