N-(tert-butoxycarbonyl)-3-(trimethylsilyl)-2-propynylamine | 71592-57-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-(tert-butoxycarbonyl)-3-(trimethylsilyl)-2-propynylamine
• 英文别名: 3-trimethylsilyl-N-tert-butoxycarbonyl-prop-2-ynylamine；3-trimethylsilyl-N-t-butoxycarbonylprop-2-ynylamine；BocHNCH2CCSiMe3；tert-Butyl (3-(trimethylsilyl)prop-2-yn-1-yl)carbamate；tert-butyl N-(3-trimethylsilylprop-2-ynyl)carbamate
• CAS: 71592-57-9
• 化学式: C₁₁H₂₁NO₂Si
• 分子量: 227.379
• InChiKey: ALZMLNAEPLSHIB-UHFFFAOYSA-N

物化性质

• 熔点：
  61 °C
• 沸点：
  269.7±23.0 °C(Predicted)
• 密度：
  0.941±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.39
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(tert-butoxycarbonyl)-3-(trimethylsilyl)-2-propynylamine 生成 [1-[(2-methylpropan-2-yl)oxycarbonylamino]-3-trimethylsilylprop-2-ynyl] acetate
  参考文献：
  名称：

  METCALF B. W.; CASARA P., J. CHEM. SOC. CHEM. COMUN., 1979, NO 3, 119-120

  摘要：

  DOI：
• 作为产物：
  描述：

  3-溴-1-三甲基硅基-1-丙炔 在 potassium carbonate 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.33h， 生成 N-(tert-butoxycarbonyl)-3-(trimethylsilyl)-2-propynylamine
  参考文献：
  名称：

  氮杂

  摘要：

  在烯丙基胺前体中包含C-2三烷基甲硅烷基取代基可以使碱诱导的aza- [2,3] -Wittigσ重排以优异的收率和非对映选择性进行。重排前体需要基于羰基的氮保护基团，该基团必须对反应所需的过量强碱稳定。N-Boc和N-苯甲酰基在稳定产物阴离子和引发去质子方面非常出色。迁移基团（G）需要通过共振来稳定初始阴离子，并且需要G-CH（3）（）pK（a）> 22，以便初始阴离子具有足够的反应性以进行重排。产物7、20b-d，f，g和23以高（10-20：1）抗非对映选择性形成。含有吗啉酰胺基的产物23可用于制备其他羰基衍生物。

  DOI：

  10.1021/jo0056343

文献信息

• Unstabilized Azomethine Ylides for the Stereoselective Synthesis of Substituted Piperidines, Tropanes, and Azabicyclo[3.1.0] Systems
  作者：Michael A. Ischay、Michael K. Takase、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja312311k

  日期：2013.2.20

  azomethine ylides that can (1) be protonated and reduced with high stereoselectivity to give piperidines, (2) participate in [3 + 2] dipolar cycloaddition to give tropanes, and (3) undergo a Nazarov-like 6-π electrocyclization that upon reduction give 2-azabicyclo[3.1.0] systems.

  密集取代的 2-甲硅烷基-1,2-二氢吡啶的酸处理为反应性偶氮甲碱叶立德提供了一种新的方便的入口，可以 (1) 以高立体选择性质子化和还原得到哌啶，(2) 参与 [3 + 2]偶极环加成得到托烷，和 (3) 经历类似纳扎罗夫的 6-π 电环化，还原后得到 2-氮杂双环 [3.1.0] 系统。
• Regioselective synthesis of highly functionalized alkenylboronates by Cu-catalyzed borylation of propargylic silylalkynes
  作者：Yeong Eun Kim、DingXi Li、Jaesook Yun

  DOI：10.1039/c5dt00144g

  日期：——

  High regioselectivity was achieved in the Cu(I)-catalyzed borylation of internal propargylic alkynes with a silyl substituent to afford multifunctionalized alkenylboron compounds. While both the silyl and propargylic substituents are known to act as directing groups, a N-heterocyclic carbene (NHC)–Cu complex furnished β-vinylboronate products (relative to Si) with high selectivity.

  在内部炔丙基炔烃与甲硅烷基取代基的Cu（I）催化的硼化中获得了高区域选择性，从而提供了多官能化的烯基硼化合物。众所周知，甲硅烷基和炔丙基取代基都可以作为导向基团，而N-杂环卡宾（NHC）-Cu络合物可提供高选择性的β-乙烯基硼酸酯产品（相对于Si）。
• Carboxylate-Catalyzed <i>C</i>-Silylation of Terminal Alkynes
  作者：Anton Bannykh、Petri M. Pihko

  DOI：10.1021/acs.orglett.3c04213

  日期：2024.3.15

  carboxylate-catalyzed, metal-free C-silylation protocol for terminal alkynes is reported using a quaternary ammonium pivalate as the catalyst and commercially available N,O-bis(silyl)acetamides as silylating agents. The reaction proceeds under mild conditions, tolerates a range of functionalities, and enables concomitant O- or N-silylation of acidic OH or NH groups. A Hammett ρ value of +1.4 ± 0.1 obtained for

  据报道，使用新戊酸季铵作为催化剂和市售的N ， O-双(甲硅烷基)乙酰胺作为甲硅烷基化剂，用于末端炔烃的羧酸盐催化的、无金属的C-甲硅烷基化方案。该反应在温和条件下进行，可耐受一系列官能团，并能够同时进行酸性 OH 或 NH 基团的O - 或N -甲硅烷基化。对位取代的 2-芳基炔获得的 Hammett ρ 值为 +1.4 ± 0.1，这与所提出的涉及决定转换的去质子化步骤的催化循环一致。
• Syntheses of proline analogs as potential mechanism-based inhibitors of proline dehydrogenase: 4-methylene-L-, (E)- and (Z)-4-(fluoromethylene)-L-, cis- and trans-5-ethynyl-(.+-.)-, and cis- and trans-5-vinyl-L-proline
  作者：Franco Manfre、Jean Marc Kern、Jean Francois Biellmann

  DOI：10.1021/jo00033a029

  日期：1992.3

  Proline dehydrogenase is an enzyme involved in the energetic processes required for flight in certain insects including the tse-tse fly. Proline analogues were designed for the inhibition of this enzyme. For this purpose 4-methylene-L-proline and (E)- and (Z)-4-(fluoromethylene)-L-proline were prepared from trans-4-hydroxyl-L-proline through the following sequence: protection at the nitrogen with a tert-butoxycarbonyl and at the caboxylic acid as methyl ester, oxidation of the hydroxyl group to a ketone, Wittig reaction, and removal of the protecting groups. The cis- and trans-5-ethynyl-(+/-)-proline was prepared from N-(tert-butoxycarbonyl)-3-(trimethylsilyl)-2-propynylamine whose dianion reacted with 1,2-epoxy 4-bromobutane. Cyclization in the presence of trifluoroacetic acid, oxidation of the primary alcohol to acid, and removal of the protecting groups gave cis- and trans-5-ethynyl-(+/-)-proline. Stereoselectivity was observed in the reaction of the dianion of 3-(trimethylsilyl)-2-propynylamine with 1,2-epoxy-4-bromobutane. The cis- and trans-5-vinyl-L-prolines were prepared from N-(methoxycarbonyl)-5-methoxy-L-proline ester by reaction with bis(trimethylsilyl)acetylene in the presence of titanium tetrachloride followed by sequential removal of the protecting groups and by reduction. The cis and trans configuration of the 5-vinyl-L-proline obtained was established by comparison of the NMR spectrum of the trans-N-tosyl-5-vinyl-(+/-)-proline methyl ester with the published spectrum of the trans derivative.
• Casara, Patrick; Danzin, Charles; Metcalf, Brian, Journal of the Chemical Society. Perkin transactions I, 1985, p. 2201 - 2208
  作者：Casara, Patrick、Danzin, Charles、Metcalf, Brian、Jung, Michel

  DOI：——

  日期：——