N-Benzyl-N-<(trimethylsilyl)methyl>benzamide | 91003-36-0

• 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: N-Benzyl-N-<(trimethylsilyl)methyl>benzamide
• 英文别名: N-benzyl-N-(trimethylsilylmethyl)benzamide
• CAS: 91003-36-0
• 化学式: C₁₈H₂₃NOSi
• 分子量: 297.472
• InChiKey: PLYSYOZQOFYGOH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.21
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-Benzyl-N-<(trimethylsilyl)methyl>benzamide 在 cesium fluoride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 14.0h， 生成 Methyl N-benzyl-2-phenylpyrrole-3-carboxylate
  参考文献：
  名称：

  Generation of azomethine ylides via the desilylation reaction of immonium salts

  摘要：

  DOI：

  10.1021/jo00192a013
• 作为产物：
  描述：

  碘甲基三甲基硅烷 、 n-苄基苯甲酰胺 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以65%的产率得到N-Benzyl-N-<(trimethylsilyl)methyl>benzamide
  参考文献：
  名称：

  Investigations of Novel Azomethine Ylide-Forming Photoreactions of N-Silylmethylimides

  摘要：

  The scope of a recently discovered (Yoon, E. C. et al. J. Am. Chem. Sec. 1995, 117, 2698), azomethine ylide-forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. Photolysis of N-[(trimethylsilyl)methyl]maleimide (4) in acetonitrile leads to efficient production of the tricyclic product 16, formed by trapping of the photogenerated azomethine ylide intermediate 15 through cydoaddition with 4. Irradiation 4 in solutions containing high concentrations of the dipolarophiles, acrylonitrile or fumaronitrile, results in production of the products (19-21 and 23-24, respectively) arising by cycloaddition of the ylide 15 with the added dipolarophiles. In contrast, photolysis of the nonconjugated cyclic imide, N-[(trimethylsilyl)methyl]succinimide (5), brings about N-acyl migration resulting in the exclusive production of the unstable, iminolactone 30. On the other hand, acyclic, N-trimethylsilylmethyl aroyl imides 6-8 undergo the excited state C to O silyl migration reaction to produce azomethine ylide intermediates 35. Both in the presence or absence of added dipolarophiles, these ylides undergo electrocyclization to form transient aziridine intermediates 36 which react further by ring opening to generate N-phenacylamide products 32-34. In contrast, the nonconjugated imide, N-[(trimethylsilyl)methyl]-N-acetylacetamide (9), is unreactive upon irradiation. Similarly, simple N-[(trimethylsilyl)methyl] amides 10-13, while being photochemically labile, do not react to form ''trappable'' ylide intermediates upon irradiation. The results outlined above are presented and discussed in terms of the scope and limitations of the new, azomethine ylide-forming photoreaction of silylmethyl imides.

  DOI：

  10.1021/jo00113a012

文献信息

• General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides and Lactams
  作者：Ken Yamazaki、Pablo Gabriel、Graziano Di Carmine、Julia Pedroni、Mirxan Farizyan、Trevor A. Hamlin、Darren J. Dixon

  DOI：10.1021/acscatal.1c01589

  日期：2021.6.18

  accessible. Subsequent regio- and diastereoselective, inter- and intramolecular dipolar cycloaddition reactions with variously substituted electron-deficient alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies

  描述了稳定和不稳定偶氮甲碱叶立德的铱催化还原生成及其在通过 [3 + 2] 偶极环加成反应合成功能化吡咯烷中的应用。在温和的反应条件下，使用 1 mol% Vaska 配合物 [IrCl(CO)(PPh 3 ) 2，从具有适当位置的吸电子或三甲基甲硅烷基的酰胺和内酰胺前体进行反应] 和四甲基二硅氧烷 (TMDS) 作为末端还原剂，可以使用范围广泛的（未）稳定的偶氮甲碱叶立德。随后的区域选择性和非对映选择性、分子间和分子内偶极环加成反应与各种取代的缺电子烯烃能够快速有效地获得结构复杂的吡咯烷结构。偶极环加成反应的密度泛函理论 (DFT) 计算揭示了过渡结构的异步性和相互作用能之间的密切平衡，这最终控制了在某些情况下观察到的异常选择性。
• PADWA, A.;HAFFMANNS, G.;TOMAS, M., J. ORG. CHEM., 1984, 49, N 8, 3314-3322
  作者：PADWA, A.、HAFFMANNS, G.、TOMAS, M.

  DOI：——

  日期：——
• Investigations of Novel Azomethine Ylide-Forming Photoreactions of N-Silylmethylimides
  作者：Ung Chan Yoon、Sung Ju Cho、Yean-Jang Lee、Maria J. Mancheno、Patrick S. Mariano

  DOI：10.1021/jo00113a012

  日期：1995.4

  The scope of a recently discovered (Yoon, E. C. et al. J. Am. Chem. Sec. 1995, 117, 2698), azomethine ylide-forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. Photolysis of N-[(trimethylsilyl)methyl]maleimide (4) in acetonitrile leads to efficient production of the tricyclic product 16, formed by trapping of the photogenerated azomethine ylide intermediate 15 through cydoaddition with 4. Irradiation 4 in solutions containing high concentrations of the dipolarophiles, acrylonitrile or fumaronitrile, results in production of the products (19-21 and 23-24, respectively) arising by cycloaddition of the ylide 15 with the added dipolarophiles. In contrast, photolysis of the nonconjugated cyclic imide, N-[(trimethylsilyl)methyl]succinimide (5), brings about N-acyl migration resulting in the exclusive production of the unstable, iminolactone 30. On the other hand, acyclic, N-trimethylsilylmethyl aroyl imides 6-8 undergo the excited state C to O silyl migration reaction to produce azomethine ylide intermediates 35. Both in the presence or absence of added dipolarophiles, these ylides undergo electrocyclization to form transient aziridine intermediates 36 which react further by ring opening to generate N-phenacylamide products 32-34. In contrast, the nonconjugated imide, N-[(trimethylsilyl)methyl]-N-acetylacetamide (9), is unreactive upon irradiation. Similarly, simple N-[(trimethylsilyl)methyl] amides 10-13, while being photochemically labile, do not react to form ''trappable'' ylide intermediates upon irradiation. The results outlined above are presented and discussed in terms of the scope and limitations of the new, azomethine ylide-forming photoreaction of silylmethyl imides.
• Generation of azomethine ylides via the desilylation reaction of immonium salts
  作者：Albert Padwa、Gunter Haffmanns、Miguel Tomas

  DOI：10.1021/jo00192a013

  日期：1984.9