3,N-bis(trimethylsilyl)propargylamine | 120420-01-1

• 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: 3,N-bis(trimethylsilyl)propargylamine
• 英文别名: bis-(trimethylsilyl)propargylimine；N,3-bis(trimethylsilyl)-2-propyn-1-imine；(E)-N,3-bis(trimethylsilyl)prop-2-yn-1-imine
• CAS: 120420-01-1
• 化学式: C₉H₁₉NSi₂
• 分子量: 197.428
• InChiKey: UNQWFEWGIVECTP-CSKARUKUSA-N

物化性质

• 沸点：
  40-50 °C(Press: 0.1 Torr)
• 密度：
  0.77±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-二乙基氨基乙酸乙酯 、 3,N-bis(trimethylsilyl)propargylamine 生成 trans-3-(N,N-diethylamino)-4-<(trimethylsilyl)ethynyl>-2-azetidinone
  参考文献：
  名称：

  A new and efficient route to 3-amino-2-azetidinones via zinc enolates of N,N-disubstituted glycine esters

  摘要：

  This report describes novel and efficient ''one-pot'' syntheses of 1-unsubstituted-3-amino-4-substituted-2-azetidinones (8 and 9) involving the in situ preparation of lithium and particularly zinc enolates (5 and 6, respectively) of N,N-disubstituted glycine esters (4) and subsequent reactions of these enolates with (simple) imines (7). Lithium enolates 5 only react with activated imines that are N-substituted with an electron-withdrawing group (e.g. aryl, trialkylsilyl), affording cis-3-amino-2-azetidinones in excellent yields with moderate to good stereoselectivity (de 68-92%). Zinc enolates 6 are more generally applicable since they react with activated imines as well as unactivated imines (e.g. those which are N-substituted with an electron-donating group such as alkyl) to afford 3-amino-2-azetidinones in excellent yields. The trans diastereoselectivity of the zinc-mediated enolate-imine condensation can be tuned by changing the steric and electronic properties of the substituents of the reagents (i.e. both enolate and imine), as well as the solvent polarity. The observed stereoselectivities are explained in terms of two highly ordered transition states, consisting of a Z-zinc ester enolate and an E-imine. Protection of the amino function of the metal enolates as a 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane ring affords 2-azetidinone products that can be easily deprotected to provide a free 3-amino function. In this way, trans-1-benzyl-3-(protected amino)-4-methyl-2-azetidinone (9a) and trans-3-(protected amino)-4-[(trimethylsilyl)ethynyl]-2-azetidinone (9g), key intermediates in the synthesis of Aztreonam (and 9g for bicyclic beta-lactam antibiotics as well), have been prepared in excellent yields (98 and 93%, respectively) with a high diastereoselectivity (de 82 and 94%, respectively). Furthermore, depending on the reactivity of imines 7, our method is also applicable using a catalytic amount (10 mol %) of ZnCl2.

  DOI：

  10.1021/jo00017a030
• 作为产物：
  描述：

  六甲基二硅烷 、 3-三甲基甲硅烷基丙炔醛 在 正丁基锂 、 三甲基氯硅烷 作用下， 生成 3,N-bis(trimethylsilyl)propargylamine
  参考文献：
  名称：

  硅辅助合成β-内酰胺

  摘要：

  -甲硅烷基亚胺与甲硅烷基乙烯酮缩醛在ZnI 2和叔丁醇的存在下反应，然后用MeMgBr处理中间体-甲硅烷基β-氨基酯，以高收率产生-甲硅烷基-氮杂环丁烷-2-酮。在某些情况下，使用三氟甲磺酸三甲基甲硅烷基酯作为路易斯酸催化剂可能是有利的。在此上下文中，详细描述了乙醛酸乙酯的叔丁基二甲基甲硅烷基亚胺的制备。

  DOI：

  10.1016/s0040-4020(01)86663-1

文献信息

• Selective formation of 1,3,4-trisubstituted and 3,4-disubstituted trans-β-lactams from zinc enolates and imines
  作者：Johann T. B. H. Jastrzebski、Fred H. van der Steen、Gerard van Koten

  DOI：10.1002/recl.19871060910

  日期：——

  synthesis (better then 90%) of exclusively trans-β-lactams (azetidin-2-ones) is reported which involves the 1:1 reaction of an α-aminoacid ester zinc enolate with an appropriate imine. The reaction can be carried out as a ‘one-pot’ synthesis as has been demonstrated for the synthesis of trans-3-diethylamino-4-phenyl azetidin-2-one (93% yield). The novel zinc enolates have most likely a Z-geometry as a result

  据报导一种高产率合成（最好是90％以上）的反式-β-内酰胺类化合物（azetidin-2-ones）的新方法，该方法涉及α-氨基酸酯烯醇锌与适当的亚胺的1：1反应。该反应可以作为“一锅法”合成进行，正如合成反式-3-二乙基氨基-4-苯基氮杂环丁烷-2-酮所证明的那样（93％收率）。由于分子内螯合物的配位，新型的烯醇锌很可能具有Z-几何形状。已经获得的证据是，在第一步中，这些烯醇锌以高度非对映选择性的方式与亚胺反应，提供苏式醛缩醛酸酯，在随后的步骤中将其闭环成氮杂环丁烷-2-酮。
• (<i>3R</i>)-Chiral Control of 3-Alkyl-3-hydroxy-β-lactams via Addition Reaction of Imines to Enolates of 1,3-Dioxolan-4-ones
  作者：Gaetano Barbaro、Arturo Battaglia、Andrea Guerrini、Carlo Bertucci

  DOI：10.1021/jo9822481

  日期：1999.6.1

  self-regeneration of stereocenters and has been applied to addition reactions among a selected number of imines and (2S)-chiral enolates of 1,3-dioxolan-4-ones. These reagents are easily available from the acetalization of (S)-alpha-hydroxy acids (lactic, mandelic, isovaleric, malic) and pivalaldehyde or pinacolone. In several cases, the addition of the enolate to the imine, the cyclization, and the removal of

  描述了一种以通用且可预测的方式手性构建（3R）-3-烷基-3-羟基-β-内酰胺的方法。该方案遵循Seebach立体中心自我再生的合成原理，并已应用于选定数量的1，3-二氧杂戊环-4-酮亚胺和（2S）-手性烯酸酯之间的加成反应。这些试剂很容易从（S）-α-羟基酸（乳酸，扁桃，异戊酸，苹果酸）和新戊醛或频哪酮的缩醛化中获得。在某些情况下，将烯酸酯添加到亚胺中，环化并去除辅助中心是一步一步完成的，提供了相应的β-内酰胺，如（3R，4S）-Z和（3R，4R ）-E对映体过量的非对映体混合物。四个带有2-呋喃基（4e）的N-未取代的（3R，4S）-3-羟基-3-甲基-β-内酰胺，获得C4处的苯基乙烯基（4h），甲氧基羰基（4i）和2-噻吩基（4l）取代基作为主要的非对映异构体，并通过结晶纯化。这些取代基同时存在于C3和C4处，使这些β-内酰胺成为合成新紫杉烷类的有用中间体，新的紫杉类化合物在异丝氨酸部分具有有趣的结构修饰。
• VAN, DER STEEN FRED H.;KLEIJN, HENK;JASTRZEBSKI, JOHANN T. B. H.;VAN, KOT+, TETRAHEDRON LETT., 30,(1989) N, C. 765-768
  作者：VAN, DER STEEN FRED H.、KLEIJN, HENK、JASTRZEBSKI, JOHANN T. B. H.、VAN, KOT+

  DOI：——

  日期：——
• HART, D. J.;KANAI, KEN-ICHI;TOHOMAS, D. G.;YANG, TENG-KUEI, J. ORG. CHEM., 1983, 48, N 3, 289-294
  作者：HART, D. J.、KANAI, KEN-ICHI、TOHOMAS, D. G.、YANG, TENG-KUEI

  DOI：——

  日期：——
• COLVIN, E. W.;MCGARRY, D. G., J. CHEM. SOC. CHEM. COMMUN., 1985, N 9, 539-540
  作者：COLVIN, E. W.、MCGARRY, D. G.

  DOI：——

  日期：——