(E)-4-dimethylphenylsilyl-2,2,7,7-tetramethyl-3-octen-5-yne

• 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: (E)-4-dimethylphenylsilyl-2,2,7,7-tetramethyl-3-octen-5-yne
• 英文别名: (E)-4-Dimethylphenylsilyl-2,2,7,7-tetramethyl-3-octen-5-in；dimethyl-phenyl-[(E)-2,2,7,7-tetramethyloct-3-en-5-yn-4-yl]silane
• 化学式: C₂₀H₃₀Si
• 分子量: 298.544
• InChiKey: XVJTZPDCXLWSTD-FBMGVBCBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.16
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  2,2,7,7-四甲基-3,5-辛二炔 、 二甲基苯基硅烷 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer chiral phosphine derivative 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以56%的产率得到(E)-4-dimethylphenylsilyl-2,2,7,7-tetramethyl-3-octen-5-yne
  参考文献：
  名称：

  金属催化氢化硅烷化的光学活性烯的新不对称合成

  摘要：

  描述了在手性膦配体存在下，Rh和Ni催化的丁二炔向手性烯的氢化硅烷化。首次使用[Rh（COD）Cl] 2 /（-）-PPM达到了27％的对映体过量，使用NiCl 2 [（-）-DIOP]达到了11％的对映体过量。

  DOI：

  10.1016/s0022-328x(00)00206-0

文献信息

• Catalytic asymmetric hydrosilylation of butadiynes: A new synthesis of optically active allenes
  作者：Annegret Tillack、Dirk Michalik、Cornelia Koy、Manfred Michalik

  DOI：10.1016/s0040-4039(99)01403-3

  日期：1999.9

  The Rh-catalyzed hydrosilylation of butadiynes to chiral allenes in the presence of chiral phosphine ligands is described. For the first time an enantiomeric excess of 22% was achieved using PPM ligand ((2S,4S)-(−)-4-(diphenylphosphino)-2-(diphenylphosphinomethyl)-pyrrolidine).

  描述了在手性膦配体存在下丁二炔的Rh催化的氢化硅烷化为手性烯丙基。使用PPM配体（（2 S，4 S）-（-）-4-（二苯基膦基）-2-（二苯基膦基甲基）-吡咯烷）首次实现了22％的对映体过量。
• Hydrosilylierung von symmetrisch disubstituierten Alkinen und Butadiinen mit L2Ni(0)-Butadiin-Komplexen [L  Ph3P, (o-Tol-O)3P] als Katalysatoren
  作者：A. Tillack、S. Pulst、W. Baumann、H. Baudisch、K. Kortus、U. Rosenthal

  DOI：10.1016/s0022-328x(96)06734-4

  日期：1997.4

  The hydrosilatation of Pr-n-C=C-Pr-n, Ph-C=C-Ph, Me3Si-C=C-SiMe3, Ph-C=C-C=C-Ph, Bu-t-C=C-C=C-Bu-t and Me3Si-C=C-C=C-SiMe3 with Ph2SiH2, PhMe2SiH and Et3SiH in the presence of L2Ni(0)-butadiyne catalysts [L = Ph3P, (o-Tol-O)(3)P] has been studied. In all cases the hydrosilylation proceeds via a cis-addition of the silanes. The disubstituted alkynes (Pr-n-C=C-Pr-n, Ph-C=C-Ph) give hydrosilylated ethene, butadiene and hexatriene derivatives as well as non-hydrosilylated benzene derivatives. In the case of Me3Si-C=C-SiMe3 no reaction was observed. The hydrosilylation of disubstituted butadiynes proceeds stepwise to give at first the 1,2-adducts. In dependence on the butadiynes either a 1,4-addition (Bu-t-C=C-C=C-Bu-t, Me3Si-C=C-C=C-SiMe3) to the corresponding allene derivatives (11, 13, 15) or a 3,4-addition (Ph-C=C-C=C-Ph) to the 1,3-butadiene 19 takes place subsequently. The reaction products were characterized by mass spectrometry, IR and NMR spectroscopy.
• A new asymmetric synthesis of optically active allenes via metal catalyzed hydrosilylation
  作者：Annegret Tillack、Cornelia Koy、Dirk Michalik、Christine Fischer

  DOI：10.1016/s0022-328x(00)00206-0

  日期：2000.5

  The Rh and Ni catalyzed hydrosilylation of butadiynes to chiral allenes in the presence of chiral phosphine ligands is described. For the first time an enantiomeric excess up to 27% was achieved using [Rh(COD)Cl]2/(−)-PPM and up to 11% using NiCl2[(−)-DIOP].

  描述了在手性膦配体存在下，Rh和Ni催化的丁二炔向手性烯的氢化硅烷化。首次使用[Rh（COD）Cl] 2 /（-）-PPM达到了27％的对映体过量，使用NiCl 2 [（-）-DIOP]达到了11％的对映体过量。