N-methyl-N-<(trimethylsilyl)methyl>-2-thiophenecarboxamide | 143266-40-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: N-methyl-N-<(trimethylsilyl)methyl>-2-thiophenecarboxamide
• 英文别名: 2-Thiophenecarboxamide, N-methyl-N-[(trimethylsilyl)methyl]-；N-methyl-N-(trimethylsilylmethyl)thiophene-2-carboxamide
• CAS: 143266-40-4
• 化学式: C₁₀H₁₇NOSSi
• 分子量: 227.403
• InChiKey: VMYLIXXLTGPCEE-UHFFFAOYSA-N

物化性质

• 沸点：
  311.6±22.0 °C(Predicted)
• 密度：
  1.036±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  48.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-methyl-N-<(trimethylsilyl)methyl>-2-thiophenecarboxamide 在 六甲基磷酰三胺 、 lithium aluminium tetrahydride 、 正丁基锂 、 cesium fluoride 作用下， 以 乙醚 、 乙腈 为溶剂， 反应 1.5h， 生成 3-<(dimethylamino)methyl>-2-methylthiophene
  参考文献：
  名称：

  Rearrangement of dimethyl(furylmethyl)ammonium and dimethyl(thienylmethyl)ammonium N-methylides. Isolation and reaction of nonaromatic intermediates

  摘要：

  3-[(Dimethylamino)methyl]-2-methylene-2,3-dihydrofuran (5o) and 2-[(dimethylamino)methyl]-3-methylene-2,3-dihydrofuran (12o) and their thiophene analogues 5s and 12s were prepared in high yields by fluoride-ion induced desilylation of NN-dimethyl-N-[(trimethylsilyl)methyl](2-furylmethyl)ammonium (3o) and -(3-furylmethyl)ammonium iodides (10o) and their thienylmethyl analogues 3s and 10s. Compound 59 or 12s was successfully converted to 3-[(dimethylamino)methyl](2-thienylmethyl)lithium (23s) or 2-[(dimethyl-amino)methyl](3-thienylmethyl)lithium (26s), which reacted with aldehydes to give [(dimethylamino)-methyl)(2-hydroxyalkyl)thiophenes 259 or 27s, respectively.

  DOI：

  10.1021/jo00046a025
• 作为产物：
  描述：

  2-噻吩甲酰氯 、 N-(trimethylsilylmethyl)methylamine 在 sodium hydroxide 作用下， 以96%的产率得到N-methyl-N-<(trimethylsilyl)methyl>-2-thiophenecarboxamide
  参考文献：
  名称：

  Rearrangement of dimethyl(furylmethyl)ammonium and dimethyl(thienylmethyl)ammonium N-methylides. Isolation and reaction of nonaromatic intermediates

  摘要：

  3-[(Dimethylamino)methyl]-2-methylene-2,3-dihydrofuran (5o) and 2-[(dimethylamino)methyl]-3-methylene-2,3-dihydrofuran (12o) and their thiophene analogues 5s and 12s were prepared in high yields by fluoride-ion induced desilylation of NN-dimethyl-N-[(trimethylsilyl)methyl](2-furylmethyl)ammonium (3o) and -(3-furylmethyl)ammonium iodides (10o) and their thienylmethyl analogues 3s and 10s. Compound 59 or 12s was successfully converted to 3-[(dimethylamino)methyl](2-thienylmethyl)lithium (23s) or 2-[(dimethyl-amino)methyl](3-thienylmethyl)lithium (26s), which reacted with aldehydes to give [(dimethylamino)-methyl)(2-hydroxyalkyl)thiophenes 259 or 27s, respectively.

  DOI：

  10.1021/jo00046a025

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。
• Rearrangement of dimethyl(furylmethyl)ammonium and dimethyl(thienylmethyl)ammonium N-methylides. Isolation and reaction of nonaromatic intermediates
  作者：Takeshi Usami、Naohiro Shirai、Yoshiro Sato

  DOI：10.1021/jo00046a025

  日期：1992.9

  3-[(Dimethylamino)methyl]-2-methylene-2,3-dihydrofuran (5o) and 2-[(dimethylamino)methyl]-3-methylene-2,3-dihydrofuran (12o) and their thiophene analogues 5s and 12s were prepared in high yields by fluoride-ion induced desilylation of NN-dimethyl-N-[(trimethylsilyl)methyl](2-furylmethyl)ammonium (3o) and -(3-furylmethyl)ammonium iodides (10o) and their thienylmethyl analogues 3s and 10s. Compound 59 or 12s was successfully converted to 3-[(dimethylamino)methyl](2-thienylmethyl)lithium (23s) or 2-[(dimethyl-amino)methyl](3-thienylmethyl)lithium (26s), which reacted with aldehydes to give [(dimethylamino)-methyl)(2-hydroxyalkyl)thiophenes 259 or 27s, respectively.