(Z)-2-(dimethylphenylsilylmethyl)-2-octenal | 144776-78-3

• 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: (Z)-2-(dimethylphenylsilylmethyl)-2-octenal
• 英文别名: (Z)-2-dimethylphenylsilylmethyloct-2-enal；(Z)-2-[[dimethyl(phenyl)silyl]methyl]oct-2-enal
• CAS: 144776-78-3
• 化学式: C₁₇H₂₆OSi
• 分子量: 274.478
• InChiKey: ZCBDLFMUSBJUQO-WJDWOHSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (Z)-N-(1-adamantyl)-2-[[dimethyl(phenyl)silyl]methyl]oct-2-en-1-imine 在 aluminum oxide 、 水 作用下， 以 正己烷 、 乙酸乙酯 为溶剂， 以250 mg的产率得到(Z)-2-(dimethylphenylsilylmethyl)-2-octenal
  参考文献：
  名称：

  Synthesis of α-Silylmethyl-α,β-Unsaturated Imines by the Rhodium-Catalyzed Silylimination of Primary-Alkyl-Substituted Terminal Alkynes

  摘要：

  In contrast to our previous report on the rhodium-catalyzed reaction of terminal alkynes with equimolar amounts of hydrosilanes and isocyanides leading to (E)- or (Z)-β-silyl-α,β-unsaturated imines A, the addition of an excess molar amount of hydrosilanes relative to isocyanides in the reaction of primary-alkyl-substituted terminal alkynes results in the production of α-silylmethyl-α,β-unsaturated imines B. Various isocyanides bearing tert-butyl and 1-adamantyl groups gave B with good product selectivity. Z isomers were formed stereoselectively in many cases. Regarding the mechanism for this reaction, when the hydrosilane was added to the reaction mixture in two portions, unsaturated imines A were initially formed, which then underwent double-bond isomerization, probably catalyzed by a Rh-H species, to give B.

  DOI：

  10.1021/jo501431e

文献信息

• Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals
  作者：Isamu Matsuda、Nakayoshi Niikawa、Rika Kuwabara、Hirofumi Inoue、Hideo Nagashima、Kenji Itoh

  DOI：10.1016/s0022-328x(98)00933-4

  日期：1999.2

  Propargyl-type alcohols (6) and the corresponding esters of carbonic acid (4) or acetic acid (5) react with two equivalents of Me2PhSiH in the presence of catalytic amounts of Rh-4(CO)(12) under CO pressure at 100 degrees C to give 2-(dimethylphenylsiIylmethyl)-2-alkenals (3), whereas 2-substituted-3-(dimethylphenylsilyl)propenals (7, 8 and 9) are also isolated with the concomitant formation of 3 when a similar reaction is operated with shortage of Me2PhSiH or with lowering of reaction temperature. The isolated 9 is selectively converted to 3 by the Rh-4(CO)(12) catalyzed reaction with Me2PhSiH under CO pressure. This fact suggests that the transformation of 4, 5 or 6 to 3 is accomplished by either a one-pot procedure or a stepwise procedure relayed by 7, 8 or 9. Usefulness of this protocol is demonstrated by the synthesis of 18 in which ethisterone (17) is directly converted by a one-pot procedure. (C) 1999 Elsevier Science S.A. All rights reserved.
• Rhodium catalyzed transformation of propargylamines to 2-silylmethyl-2-alkenals: Formal silylformylation of allenes
  作者：Isamu Matsuda、Jun Sakakibara、Hirofumi Inoue、Hideo Nagashima

  DOI：10.1016/0040-4039(92)89035-b

  日期：1992.9

  Propargylamines are effectively transformed to 2-dimethylphenylsilylmethyl-2-alkenals by the interaction of two equivalents of Me2PhSiH under silylformylation conditions catalyzed by Rh4(CO)12. The products are not obtained directly by silylformylation of the corresponding allenes.