(Z)-3-methyl-2-[(dimethyl-4-methoxyphenylsilyl)methylene]-3-(p-tosylamino)butanal | 875612-12-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Z)-3-methyl-2-[(dimethyl-4-methoxyphenylsilyl)methylene]-3-(p-tosylamino)butanal
• 英文别名: N-[(Z)-3-formyl-4-[(4-methoxyphenyl)-dimethylsilyl]-2-methylbut-3-en-2-yl]-4-methylbenzenesulfonamide
• CAS: 875612-12-7
• 化学式: C₂₂H₂₉NO₄SSi
• 分子量: 431.628
• InChiKey: QJGZKBUJTRAUPF-FBMGVBCBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  80.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (Z)-3-methyl-2-[(dimethyl-4-methoxyphenylsilyl)methylene]-3-(p-tosylamino)butanal 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以55%的产率得到2-(4-methoxybenzyl)-3-methylbut-2-enal
  参考文献：
  名称：

  炔丙基酰胺的甲硅烷基甲酰化-去甲硅烷基化：α，β-不饱和醛的合成

  摘要：

  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。

  DOI：

  10.1016/j.tetlet.2005.11.054
• 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 (Z)-3-methyl-2-[(dimethyl-4-methoxyphenylsilyl)methylene]-3-(p-tosylamino)butanal
  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。
• 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.