dimethyl(cyclohex-2-en-1-yl)(phenyl)silane | 146513-23-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: dimethyl(cyclohex-2-en-1-yl)(phenyl)silane
• 英文别名: cyclohex-2-en-1-yldimethyl(phenyl)silane；(2-cyclohexenyl)dimethyl(phenyl)silane；1-(dimethylphenylsilyl)cyclohex-2-ene；cyclohex-2-enyl-dimethylphenylsilane；3-(phenyldimethylsilyl)cyclohexene；3-dimethyl(phenyl)silylcyclohexene；Cyclohex-2-en-1-yl-dimethyl-phenylsilane
• CAS: 146513-23-7；87436-92-8
• 化学式: C₁₄H₂₀Si
• 分子量: 216.398
• InChiKey: STQUZUMWOPTQQC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  dimethyl(cyclohex-2-en-1-yl)(phenyl)silane 以0%的产率得到
  参考文献：
  名称：

  Fleming Ian, Lawrence Nicholas J., J. Chem. Soc. PerKin Trans. I, (1992) N 24, S 3309-3326

  摘要：

  DOI：
• 作为产物：
  描述：

  1-trifluoromethanesulfonyloxy-3-dimethylphenylsilylcyclohex-1-ene 在 甲酸 、 palladium diacetate 、 三乙胺 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以65%的产率得到dimethyl(cyclohex-2-en-1-yl)(phenyl)silane
  参考文献：
  名称：

  A Tissue-Selective Nonsteroidal Progesterone Receptor Modulator: 7,9-Difluoro-5-(3-methylcyclohex-2-enyl)-2,2,4-trimethyl-1,2-dihydrochromeno[3,4-f]quinoline

  摘要：

  The progesterone receptor plays an important role in the female reproductive system. Here we describe the discovery of a new selective progesterone receptor modulator (SPRM). In rats, the lead compound, 7,9-difluoro-5-(3-methylcyclohex-2-enyl)-2,2,4-trimethyl-1,2-dihydrochromeno[3,4-f]quinoline (5c), inhibited ovulation and showed full efficacy in uterine and vaginal tissue but was a mixed partial agonist/antagonist in breast tissue. The compound also suppressed ovulation in monkeys, but in contrast to currently approved steroidal PR agonists, it did not suppress estradiol levels.

  DOI：

  10.1021/jm8004256

文献信息

• Practical Synthesis of Allylic Silanes from Allylic Esters and Carbamates by Stereoselective Copper-Catalyzed Allylic Substitution Reactions
  作者：Martin Oestreich、Gertrud Auer

  DOI：10.1002/adsc.200404381

  日期：2005.4

  The first copper-catalyzed allylic substitution reactions of allylic acetates and carbamates employing a bis(triorganosilyl)zinc reagent are reported. This novel procedure avoids the use of stoichiometric amounts of copper salts which are usually mandatory with this chemistry. Application of this methodology to standard model substrates substantiates a high diastereoselectivity for the double bond

  报道了使用双（三有机甲硅烷基）锌试剂的第一铜催化的烯丙基乙酸酯和氨基甲酸酯的烯丙基取代反应。这种新颖的方法避免了使用化学计量的铜盐，这种化学盐通常是强制性的。该方法在标准模型基材上的应用证实了双键几何结构（E  ：  Z）和相对构型（syn  ：  anti）的高非对映选择性。
• A formal [3+2] cycloaddition for the synthesis of bicyclo[3.2.1]octanes
  作者：Crina M. Orac、Stephen C. Bergmeier

  DOI：10.1016/j.tetlet.2008.12.098

  日期：2009.3

  A new and a direct synthetic method for the construction of the bicyclo[3.2.1]octane system is envisioned by assembling cyclic allylsilanes with electron-deficient double bonds in a single step via a formal diastereoselective Lewis acid-promoted [3+2] cycloaddition.

  构想了一种新的直接合成双环[3.2.1]辛烷体系的方法，该方法是通过正规的非对映选择性路易斯酸促进的[3 + 2]环加成反应，一步一步组装具有缺电子双键的环状烯丙基硅烷。
• Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
  作者：Weichao Xue、Martin Oestreich

  DOI：10.1055/s-0037-1610309

  日期：2019.1

  shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti-dia­stereoselectivity was obtained.

  作为《五十周年综合报告》的一部分发行-黄金周年纪念日 抽象的 已显示出广泛的过渡金属催化剂可促进烯丙基亲电试剂与硅格氏试剂的烯丙基取代反应。对于CuI作为催化剂，该程序进一步进行了详细说明。区域选择性与伯烯丙基前体的离去基团无关，与α相比，α更有利。此烯丙基换位的立体化学过程，用一个环状系统探测，和抗获得-diastereoselectivity。 已显示出广泛的过渡金属催化剂可促进烯丙基亲电试剂与硅格氏试剂的烯丙基取代反应。对于CuI作为催化剂，该程序进一步进行了详细说明。区域选择性与伯烯丙基前体的离去基团无关，与α相比，α更有利。此烯丙基换位的立体化学过程，用一个环状系统探测，和抗获得-diastereoselectivity。
• Stereoselective Construction of 1,3-Disilylcyclopentane Derivatives by Scandium-Catalyzed [3+2] Cycloaddition of Allylsilanes to β-Silylenones
  作者：Kazuhiro Okamoto、Eisuke Tamura、Kouichi Ohe

  DOI：10.1002/anie.201404218

  日期：2014.9.15

  The Sc(OTf)3‐catalyzed [3+2] cycloaddition of allylsilanes to β‐silyl‐α,β‐unsaturated ketones (β‐silylenones) has been developed to form five‐membered syn‐1,3‐disilylketones diastereoselectively through the rearrangement of the silicon substituents on the allylsilane. Stabilization of the carbocation intermediates by a double silicon effect plays a key role in directing the course of the reaction to

  烯丙基硅烷的Sc（OTf）3催化的[3 + 2]环加成反应生成β-甲硅烷基-α，β-不饱和酮（β-硅烯酮），可通过非对映选择性地形成五元合成1,3-二甲硅烷基酮。烯丙基硅烷上硅取代基的重排。通过双硅效应使碳正离子中间体稳定，在指导反应过程中比简单的烯丙基化更有利于[3 + 2]环加成途径方面起着关键作用。
• Mechanistic insight into copper-catalysed allylic substitutions with bis(triorganosilyl) zincs. Enantiospecific preparation of α-chiral silanes
  作者：Eric S. Schmidtmann、Martin Oestreich

  DOI：10.1039/b606589a

  日期：——

  Isotopic desymmetrisation, as well as (stereo)chemical correlation, has illuminated significant aspects of the σ–π–σ mechanism of copper-catalysed allylic substitution reactions: an enantiospecific and regioselective access to α-chiral silanes is presented.

  同位素不对称以及（立体）化学相关性揭示了铜催化烯丙基取代反应的ÏâÏâÏ机制的重要方面：介绍了一种获得δ-手性硅烷的对映体特异性和区域选择性方法。