环己甲醇,a-[2-(二甲基苯基甲硅烷基)乙烯基]-,(E)- | 138407-92-8

• 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
• 中文名称: 环己甲醇,a-[2-(二甲基苯基甲硅烷基)乙烯基]-,(E)-
• 英文名称: (E)-1-Cyclohexyl-3-(dimethylphenylsilyl)prop-2-enol
• 英文别名: (E)-1-cyclohexyl-3-(dimethyl(phenyl)silyl)prop-2-en-1-ol；(E)-1-cyclohexyl-3-[dimethyl(phenyl)silyl]prop-2-en-1-ol
• CAS: 138407-92-8
• 化学式: C₁₇H₂₆OSi
• 分子量: 274.478
• InChiKey: OHYOOPYDZUGXMD-BUHFOSPRSA-N

物化性质

• 沸点：
  382.6±25.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.64
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  环己甲醇,a-[2-(二甲基苯基甲硅烷基)乙烯基]-,(E)- 在 chlorobis(cyclooctene)-iridium(I) dimer 、 四苯硼钠 、 sodium hydride 、 三环己基膦 作用下， 以 N,N-二甲基甲酰胺 、 氯苯 、 丙酮 为溶剂， 反应 37.0h， 生成 (2RS,3RS,E)-5-cyclohexyl-3-(dimethyl(phenyl)silyl)-2-methylpent-4-enal
  参考文献：
  名称：

  Domino Alkene-Isomerization–Claisen Rearrangement Strategy to Substituted Allylsilanes

  摘要：

  A one-pot isomerization Claisen protocol has been developed for the synthesis of highly substituted allylsilanes. Monosilylated divinyl ethers can be isomerized using a cationic iridium(I) catalyst followed by a thermal Claisen rearrangement to provide the allylsilanes in excellent yields and diastereoselectivities.

  DOI：

  10.1021/jo202560g
• 作为产物：
  描述：

  1-Cyclohexyl-3-(dimethylphenylsilyl)prop-2-ynol 在 二氯二茂钛 、 Isobutylmagnesium chloride 、 水 作用下， 生成 环己甲醇,a-[2-(二甲基苯基甲硅烷基)乙烯基]-,(E)-
  参考文献：
  名称：

  Exploring the reactivity of alkenes bearing silicon and/or tin in the hydroxyl-directed hydrogenation. A diastereoselective synthesis of heterobimetallic compounds

  摘要：

  The hydroxyl-directed hydrogenation of (E)- and (Z)-gamma-hydroxy vinylstannanes and silanes has been studied in the presence of (dppb)Rh(NBD)BF4 (1). Efficient routes to gamma-hydroxy stannanes and silanes have been developed. Diastereoselectivities from 60 to >500:1 were observed. A significant difference in reaction rate and pathway was observed between the (E)- and (Z)-vinylstannanes. We observed a reductive destannation process for the (Z)-stannanes which was influenced by the size of the R group. Competition studies were carried out to determine if steric or electronic effects were responsible for the reactivity patterns observed.

  DOI：

  10.1021/jo00100a023

文献信息

• Platinum catalysed hydrosilylation of propargylic alcohols
  作者：Catherine A. McAdam、Mark G. McLaughlin、Adam J. S. Johnston、Jun Chen、Magnus W. Walter、Matthew J. Cook

  DOI：10.1039/c3ob40496j

  日期：——

  A facile and user-friendly protocol has been developed for the selective synthesis of E-vinyl silanes derived from propargylic alcohols using a PtCl2/XPhos catalyst system. The reaction is generally high yielding and provides a single regioisomer at the β-position with E-alkene geometry. The reaction is extremely tolerant of functionality and has a wide scope of reactivity both in terms of alkynes

  已经开发了一种简便且用户友好的协议，用于使用PtCl 2 / XPhos催化剂系统选择性合成衍生自炔丙醇的E-乙烯基硅烷。该反应通常是高产率的，并且在具有E-烯烃几何构型的β-位提供单一的区域异构体。该反应对功能性极宽容，并且在所用炔烃和硅烷方面都具有广泛的反应性。已经研究了催化剂的负载量，发现在极低的催化剂负载量下观察到良好的反应性。这种方法也已扩展到丹麦-Hiyama一锅加氢硅烷化反应。
• PtCl2/XPhos: A highly efficient and readily available catalyst for the hydrosilylation of propargylic alcohols
  作者：Mark G. McLaughlin、Matthew J. Cook

  DOI：10.1039/c1cc14433b

  日期：——

  A highly regioselective hydrosilylation of propargylic alcohols has been developed using an in situ prepared PtCl(2)/XPhos catalyst system. The reaction is tolerant of many functional groups and exhibits excellent regio and geometric selectivity.

  使用原位制备的PtCl（2）/ XPhos催化剂系统开发了炔丙醇的高度区域选择性氢化硅烷化反应。该反应可耐受许多官能团，并具有出色的区域和几何选择性。
• Base-Mediated Cascade Rearrangements of Aryl-Substituted Diallyl Ethers
  作者：Jolene P. Reid、Catherine A. McAdam、Adam J. S. Johnston、Matthew N. Grayson、Jonathan M. Goodman、Matthew J. Cook

  DOI：10.1021/jo502403n

  日期：2015.2.6

  Two base-mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig–oxy-Cope and isomerization–Claisen rearrangements. Both diaryl and arylsilyl-substituted 1,3-substituted propenyl substrates were examined, and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted, which demonstrated

  开发了两个碱基介导的二烯丙基醚的级联重排反应，从而导致选择性的[2,3] -Wittig-oxy-Cope和异构化-Claisen重排。对二芳基和芳基甲硅烷基取代的1,3-取代的丙烯基底物均进行了检测，每种底物均具有独特的反应性和不同的反应途径。进行了详细的机理和计算分析，表明碱和溶剂的作用是观察到的反应性和选择性的关键。交叉实验还表明，这些反应以一定程度的解离进行，并且机理途径是高度复杂的，具有多种竞争途径。
• Lautens, Mark; Zhang, ChunHao; Crudden, Cathleen M., Angewandte Chemie, 1992, vol. 104, # 2, p. 237 - 239
  作者：Lautens, Mark、Zhang, ChunHao、Crudden, Cathleen M.

  DOI：——

  日期：——