[2-Hexyl-cyclopent-2-en-(E)-ylidenemethyl]-trimethyl-silane | 127530-90-9

• 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: [2-Hexyl-cyclopent-2-en-(E)-ylidenemethyl]-trimethyl-silane
• 英文别名: [(E)-(2-hexylcyclopent-2-en-1-ylidene)methyl]-trimethylsilane
• CAS: 127530-90-9
• 化学式: C₁₅H₂₈Si
• 分子量: 236.473
• InChiKey: FWKKWAYKUNRYPO-FYWRMAATSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.48
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  ((Z)-6-Iodo-dodec-5-en-1-ynyl)-trimethyl-silane 在 水 、 叔丁基锂 作用下， 生成 [2-Hexyl-cyclopent-2-en-(E)-ylidenemethyl]-trimethyl-silane
  参考文献：
  名称：

  炔烃衍生物的立体选择性环状碳锂化。立体选择性合成环外烯烃

  摘要：

  经由非自由基途径在δ位被锂化的（三甲基甲硅烷基）炔烃衍生物可以以立体选择性方式（≥96-98％）环化，从而以高收率得到含五元碳环的环外烯烃。

  DOI：

  10.1016/0040-4039(90)87016-s

文献信息

• Ti(II)-Mediated Allenyne Cyclization as a New Tool for Generation of Chiral Organotitanium Compounds. Asymmetric Generation of Cyclic Allyltitanium Reagents with No Chiral Auxiliary
  作者：Hirokazu Urabe、Tohru Takeda、Daigaku Hideura、Fumie Sato

  DOI：10.1021/ja972045e

  日期：1997.11.1

  Treatment of a variety of 1,2-dien-7-ynes with a slight excess of (eta(2)-propene)Ti(O-i-Pr)(2) (1), prepared in situ from Ti(O-i-Pr)(4) and 2 equiv of i-PrMgCl in ether, afforded 1-alkenyl-2-alkylidenecyclopentanes in moderate to good yields after aqueous workup. The intermediate titanabicycle such as 7 was identified by deuterolysis, which gave d(2)-8 with exclusive deuterium incorporation. The use of an optically active allene such as 19 (less than or equal to 83% ee) realized a highly efficient axial to centered chirality transfer to give 21 (80-83% ee). Analogously, the cyclization of 22 (less than or equal to 86% ee) with 1 followed by carbonylation (under ca. 1 atm of CO) afforded the optically active bicyclic ketone 25 (86% ee). When a homologous 1,2-dien-6-yne 27 was subjected to the cyclization as above, a different type of titanabicycle 28 was generated, which was identified by hydrolysis giving 29 or the following carbonyl addition. Upon reaction with nonanal, 28 afforded the alcohol 32 with very high regio-(with respect to the allylic system), stereo-(the diene moiety), and diastereoselectivities (the hydroxy group). Various 1,2-dien-6-ynes underwent the cyclization followed by the addition to carbonyl compounds in comparable selectivities as above. Chiral 1,2-dien-6-ynes 46 (less than or equal to 83% ee) achieved a nearly complete chirality transfer to generate a chiral titanabicycle 48, which, in turn, reacted with nonanal, acetone, or N-benzylidenepropylamine to afford the alcohols 51 and 52 (both in 80% ee) or the amine 53 (81% ee) in good yields with a very small loss of the enantiopurity.
• WU, GUANGZHONG;CEDERBAUM, FREDRICK E.;NEGISHI, EI-ICHI, TETRAHEDRON LETT., 31,(1990) N, C. 493-496
  作者：WU, GUANGZHONG、CEDERBAUM, FREDRICK E.、NEGISHI, EI-ICHI

  DOI：——

  日期：——