2-cyclohexylidene-3-(dimethylphenylsilyl)propanal | 144776-81-8

• 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-cyclohexylidene-3-(dimethylphenylsilyl)propanal
• 英文别名: 2-Cyclohexylidene-3-[dimethyl(phenyl)silyl]propanal
• CAS: 144776-81-8
• 化学式: C₁₇H₂₄OSi
• 分子量: 272.462
• InChiKey: ITKANSQKFQLPAA-UHFFFAOYSA-N

物化性质

• 沸点：
  392.2±35.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.06
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• 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：

  一氧化碳 、 二甲基苯基硅烷 、 炔环己醇 在 dodecacarbonyltetrarhodium(0) 作用下， 以 苯 为溶剂， 100.0 ℃ 、2.03 MPa 条件下， 反应 8.0h， 以81%的产率得到2-cyclohexylidene-3-(dimethylphenylsilyl)propanal
  参考文献：
  名称：

  Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(98)00933-4

文献信息

• 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.
• 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.