2-(dimethylphenylsilylmethyl)-3-methyl-2-butenal | 144776-79-4

• 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-(dimethylphenylsilylmethyl)-3-methyl-2-butenal
• 英文别名: 2-[[Dimethyl(phenyl)silyl]methyl]-3-methylbut-2-enal
• CAS: 144776-79-4
• 化学式: C₁₄H₂₀OSi
• 分子量: 232.398
• InChiKey: NKVHJWKEOWNTKP-UHFFFAOYSA-N

物化性质

• 沸点：
  332.9±35.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  2-甲基-3-丁炔-2-胺 在 dodecacarbonyltetrarhodium(0) sodium hydroxide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 50.0~100.0 ℃ 、3.04 MPa 条件下， 反应 24.0h， 生成 2-(dimethylphenylsilylmethyl)-3-methyl-2-butenal
  参考文献：
  名称：

  Silylation–desilylation of propargyl amides: rapid synthesis of functionalised aldehydes and β-lactams

  摘要：

  Propargyl functionalised beta-silylalkenals were easily prepared starting from suitable propargyl compounds by a silylformylation process. In particular the use of propargyl tosyl amides allowed the synthesis of alpha, beta-unsaturated aldehydes through a two-step sequence of silylformylation -desilylation reactions. TBAF was employed to induce the desilylation process that was performed under very mild experimental conditions and occurred along with an elimination step of the tosylamido moiety affording 2-methylaryl-2-alkenals with good yields and stereoselectivity. When the tosyl amides were reacted with a hydrosilane in the presence of catalytic amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) alpha-silylmethylene-beta-lactams were synthesised through a silylcarbocyclisation process. A high chemoselectivity towards the b-lactam was observed when dialkyl propargyl amides were employed. The obtained b-lactams were easily transformed into the corresponding methylaryl-b-lactams by fluoride induced aryl migration -desilylation with total retention of configuration of the migrating group and complete stereoselectivity towards the more stable b-lactam (E)-isomer. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.04.064

文献信息

• Silylformylation–desilylation of propargyl amides: synthesis of α,β-unsaturated aldehydes
  作者：Laura Antonella Aronica、Patrizio Raffa、Giulia Valentini、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1016/j.tetlet.2005.11.054

  日期：2006.1

  α,β-Unsaturated aldehydes are prepared from easily available propargyl amides through a two-step sequence of silylformylation–desilylation reactions. The substituent on the nitrogen atom markedly influences both reactions, β-silylalkenals being formed in the presence of tosyl or tert-butoxycarbonyl protected amines. TBAF is employed to induce the desilylation process that is performed under very mild

  α，β-不饱和醛是由容易获得的炔丙基酰胺通过两步的甲硅烷基甲酰化-去甲硅烷基化反应制得的。氮原子上的取代基显着影响两个反应，在甲苯磺酰基或叔丁氧羰基保护的胺存在下会形成β-甲硅烷基烯醛。TBAF用于诱导在非常温和的实验条件下进行的脱甲硅烷基化过程。当甲苯磺酰胺醛反应生成2-甲基芳基-2-烯醛时，发生了当代的消除步骤，同时可以抑制该过程，将官能团改变为NBOC，从而形成β-氨基羰基化合物。
• 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.
• Silylation–desilylation of propargyl amides: rapid synthesis of functionalised aldehydes and β-lactams
  作者：Laura Antonella Aronica、Giulia Valentini、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1016/j.tet.2007.04.064

  日期：2007.7

  Propargyl functionalised beta-silylalkenals were easily prepared starting from suitable propargyl compounds by a silylformylation process. In particular the use of propargyl tosyl amides allowed the synthesis of alpha, beta-unsaturated aldehydes through a two-step sequence of silylformylation -desilylation reactions. TBAF was employed to induce the desilylation process that was performed under very mild experimental conditions and occurred along with an elimination step of the tosylamido moiety affording 2-methylaryl-2-alkenals with good yields and stereoselectivity. When the tosyl amides were reacted with a hydrosilane in the presence of catalytic amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) alpha-silylmethylene-beta-lactams were synthesised through a silylcarbocyclisation process. A high chemoselectivity towards the b-lactam was observed when dialkyl propargyl amides were employed. The obtained b-lactams were easily transformed into the corresponding methylaryl-b-lactams by fluoride induced aryl migration -desilylation with total retention of configuration of the migrating group and complete stereoselectivity towards the more stable b-lactam (E)-isomer. (c) 2007 Published by Elsevier Ltd.