(Z)-trimethyl<(2,2-dimethylcyclopentylidene)methyl>silane | 147504-42-5

• 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: (Z)-trimethyl<(2,2-dimethylcyclopentylidene)methyl>silane
• 英文别名: [(Z)-(2,2-dimethylcyclopentylidene)methyl]-trimethylsilane
• CAS: 147504-42-5
• 化学式: C₁₁H₂₂Si
• 分子量: 182.381
• InChiKey: IZNIRRNKJUEFMM-KTKRTIGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  trimethyl(6-iodo-3,3-dimethyl-1-hexynyl)silane 在 甲醇 、 叔丁基锂 作用下， 生成 (Z)-trimethyl<(2,2-dimethylcyclopentylidene)methyl>silane
  参考文献：
  名称：

  Cyclization of acetylenic alkyllithiums

  摘要：

  The scope and limitations of cyclization reactions involving acetylenic alkyllithiums, which were prepared at -78-degrees-C by lithium-iodine exchange between the corresponding iodide and tert-butyllithium in a solution of n-pentane-diethyl ether (3:2 by volume), have been investigated. 4-Pentynyllithiums, 5-hexynyllithiums, and 6-heptynyllithiums bearing a phenyl or trimethylsilyl substituent on the triple bond undergo regiospecific exo-dig cyclization to give 4-, 5-, and 6-membered rings, respectively, bearing an exocyclic lithiomethylene moiety. Cyclization of the analogous alkyl-substituted acetylenic alkyllithiums seems to be confined to the 5-exo mode. The vinyllithium products of the cyclizations may be trapped by reaction with electrophiles to afford functionalized cycloalkylidene derivatives in good yield. The cyclization reactions were found to be highly stereoselective: intramolecular addition of the C-Li unit to the triple bond to produce 4- or 5-membered rings proceeds in a syn fashion to generate isomerically pure exocyclic vinyllithiums that may be functionalized to give stereoisomerically pure products. At the higher temperatures needed to effect cyclization of 6-heptynyllithiums, the initially formed (Z)-vinyllithium intermediate is isomerized to the more stable E-isomer which, when trapped with an electrophile, affords stereoisomerically pure product formally derived from anti addition to the triple bond.

  DOI：

  10.1021/ja00061a006

文献信息

• Atom transfer cyclization reactions of hex-5-ynyl iodides: synthetic and mechanistic studies
  作者：Dennis P. Curran、Meng Hsin Chen、Dooseop Kim

  DOI：10.1021/ja00198a043

  日期：1989.8