diisopropyl-(3-pentynyloxy)silane | 326891-18-3

• 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: diisopropyl-(3-pentynyloxy)silane
• 英文别名: [(Pent-3-yn-1-yl)oxy]di(propan-2-yl)silane；pent-3-ynoxy-di(propan-2-yl)silane
• CAS: 326891-18-3
• 化学式: C₁₁H₂₂OSi
• 分子量: 198.381
• InChiKey: JSJKTSSPLIBMRJ-UHFFFAOYSA-N

物化性质

• 沸点：
  221.8±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.96
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  diisopropyl-(3-pentynyloxy)silane 在 dihydrogen hexachloroplatinate 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 、 异丙醇 为溶剂， 反应 52.34h， 生成 (E)-3-(3-pyridyl)-3-penten-1-ol
  参考文献：
  名称：

  Intramolecular Hydrosilylation and Silicon-Assisted Cross-Coupling:  An Efficient Route to Trisubstituted Homoallylic Alcohols

  摘要：

  [GRAPHICS]Alkylidenesilacyclopentanes (formed by intramolecular hydrosilylation of homopropargyl alcohols) are efficiently coupled with aryl or alkenyl halides in the presence of tetrabutylammonium fluoride and a palladium(0) catalyst. Yields of cross-coupling were generally high, and the reaction is compatible with a wide range of functional groups. The overall transformation achieves the conversion of homopropargyl alcohols to trisubstituted homoallylic alcohols in a highly stereoselective fashion.

  DOI：

  10.1021/ol006769y
• 作为产物：
  描述：

  3-戊炔-1-醇 、 二异丙基氯代硅烷 在 三乙胺 作用下， 以 正己烷 为溶剂， 反应 0.5h， 以97%的产率得到diisopropyl-(3-pentynyloxy)silane
  参考文献：
  名称：

  串联分子内甲硅烷基甲酰基化和硅辅助交叉偶联反应。几何定义的α，β-不饱和醛的合成。

  摘要：

  报道了环甲硅烷基醚与芳基碘化物的钯和铜催化的交叉偶联反应。在一氧化碳气氛下，通过使炔丙基甲硅烷基醚2进行分子内甲硅烷基甲酰化，可以容易地制备甲硅烷基醚3。在[（烯丙基）PdCl]（2），CuI，氢硅烷和KF.2H（2）O存在下，室温下，环状甲硅烷基醚3与各种芳基碘化物7在DMF中于室温反应，得到不饱和的α，β。醛偶联产物8的收率很高。在此过程中对铜的需求表明，从硅到铜的金属转移是该机理中的重要一步。尽管硅氧烷3和产物8在碱性条件下不稳定，但KF.2H（2）O提供了对硅的反应性和降低的碱度的适当平衡。

  DOI：

  10.1021/jo034064e

文献信息

• Intramolecular Anti-Hydrosilylation and Silicon-Assisted Cross-Coupling:  Highly Regio- and Stereoselective Synthesis of Trisubstituted Homoallylic Alcohols
  作者：Scott E. Denmark、Weitao Pan

  DOI：10.1021/ol026933c

  日期：2002.11.1

  A highly regio- and stereoselective anti-intramolecular hydrosilylation of alkynyl silyl ethers catalyzed by a ruthenium arene complex has been developed. The resultant (Z)-alkylidenesilacyclopentanes are efficiently coupled with aryl or alkenyl halides in the presence of tetrabutylammonium fluoride and a palladium(0) catalyst. The yields are generally good, and the reaction is compatible with a wide

  已经开发了由钌芳烃络合物催化的炔基甲硅烷基醚的高度区域选择性和立体选择性的抗分子内氢化硅烷化。在氟化四丁基铵和钯（0）催化剂存在下，将所得的（Z）-亚烷基硅烷基环戊烷与芳基或烯基卤化物有效偶联。收率通常良好，并且该反应与多种官能团相容。总体转化实现了高炔丙醇向三取代均烯丙基醇的立体选择性转化。[反应：看文字]
• Cross-coupling reaction of organosilicon nucleophiles
  申请人：——

  公开号：US20020183516A1

  公开（公告）日：2002-12-05

  Improved methods for generating a —C—C— bond by cross-coupling of a transferable group with an acceptor group. The transferable group is a substituent of an organosilicon nucleophile and the acceptor group is provided as an organic electrophile. The reaction is catalyzed by a Group 10 transition metal complex (e.g., Ni, Pt or Pd), particularly by a palladium complex. Certain methods of this invention use improved organosilicon nucleophiles which are readily prepared, can give high product yields and exhibit high stereo selectivity. Methods of this invention employ activating ions such as halides, hydroxide, hydride and silyloxides. In specific embodiments, organosilicon nucleophilic reagents of this invention include siloxanes, particularly cyclic siloxanes. The combination of the cross-coupling reactions of this invention with ring-closing metathesis, hydrosilylation and intramolecular hydrosilylation reactions provide useful synthetic strategies that have wide application.

  本发明提供了一种通过可转移基团与受体基团的交叉偶联生成—C—C—键的改进方法。可转移基团是有机硅亲核试剂的取代基，而受体基团是有机电子亲合试剂。该反应由第10族过渡金属配合物（例如Ni、Pt或Pd），特别是钯配合物催化。本发明的某些方法使用改进的有机硅亲核试剂，这些试剂易于制备，可以产生高产率的产物，并表现出高立体选择性。本发明的方法采用卤化物、氢氧化物、氢化物和硅氧化物等活化离子。在具体实施方式中，本发明的有机硅亲核试剂包括硅氧烷，特别是环状硅氧烷。本发明的交叉偶联反应与环内闭合重聚、氢硅化和分子内氢硅化反应的结合提供了有广泛应用的有用合成策略。
• Intramolecular Hydrosilylation and Silicon-Assisted Cross-Coupling:  An Efficient Route to Trisubstituted Homoallylic Alcohols
  作者：Scott E. Denmark、Weitao Pan

  DOI：10.1021/ol006769y

  日期：2001.1.1

  [GRAPHICS]Alkylidenesilacyclopentanes (formed by intramolecular hydrosilylation of homopropargyl alcohols) are efficiently coupled with aryl or alkenyl halides in the presence of tetrabutylammonium fluoride and a palladium(0) catalyst. Yields of cross-coupling were generally high, and the reaction is compatible with a wide range of functional groups. The overall transformation achieves the conversion of homopropargyl alcohols to trisubstituted homoallylic alcohols in a highly stereoselective fashion.
• Tandem Intramolecular Silylformylation and Silicon-Assisted Cross-Coupling Reactions. Synthesis of Geometrically Defined α,β-Unsaturated Aldehydes
  作者：Scott E. Denmark、Tetsuya Kobayashi

  DOI：10.1021/jo034064e

  日期：2003.6.1

  The palladium- and copper-catalyzed cross-coupling reactions of cyclic silyl ethers with aryl iodides are reported. Silyl ethers 3 were readily prepared by intramolecular silylformylation of homopropargyl silyl ethers 2 under a carbon monoxide atmosphere. The reaction of cyclic silyl ethers 3with various aryl iodides 7 in the presence of [(allyl)PdCl](2), CuI, a hydrosilane, and KF.2H(2)O in DMF at

  报道了环甲硅烷基醚与芳基碘化物的钯和铜催化的交叉偶联反应。在一氧化碳气氛下，通过使炔丙基甲硅烷基醚2进行分子内甲硅烷基甲酰化，可以容易地制备甲硅烷基醚3。在[（烯丙基）PdCl]（2），CuI，氢硅烷和KF.2H（2）O存在下，室温下，环状甲硅烷基醚3与各种芳基碘化物7在DMF中于室温反应，得到不饱和的α，β。醛偶联产物8的收率很高。在此过程中对铜的需求表明，从硅到铜的金属转移是该机理中的重要一步。尽管硅氧烷3和产物8在碱性条件下不稳定，但KF.2H（2）O提供了对硅的反应性和降低的碱度的适当平衡。