2,7-Diphenyl-5-silaspiro<4.4>nona-2,7-diene | 133448-09-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,7-Diphenyl-5-silaspiro<4.4>nona-2,7-diene
• 英文别名: 2,7-Diphenyl-5-silaspiro[4,4]nona-2,7-diene；3,8-diphenyl-5-silaspiro[4.4]nona-2,7-diene
• CAS: 133448-09-6
• 化学式: C₂₀H₂₀Si
• 分子量: 288.464
• InChiKey: BHJYDSCCGBCJRX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.63
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  丁-1,3-二烯-2-基苯 在 四氯化硅 、 magnesium 作用下， 生成 2,7-Diphenyl-5-silaspiro<4.4>nona-2,7-diene
  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。
• Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles
  作者：Reuben D. Rieke、Heping Xiong

  DOI：10.1021/jo00009a034

  日期：1991.4

  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.