N-trimethylsilylphenylpropargylideneimine | 120420-00-0

• 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-trimethylsilylphenylpropargylideneimine
• 英文别名: N-trimethylsilylpropargylaldimine；(E)-3-phenyl-N-trimethylsilylprop-2-yn-1-imine
• CAS: 120420-00-0
• 化学式: C₁₂H₁₅NSi
• 分子量: 201.343
• InChiKey: XTKKQXWJDBCNIL-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-甲氧基-1-(三甲基甲硅氧基)-2-甲基-1-丙烯 、 N-trimethylsilylphenylpropargylideneimine 生成 3,3-dimethyl-4-(phenylethynyl)azetidin-2-one
  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
• 作为产物：
  描述：

  苯丙炔醛 、 六甲基二硅烷 在 正丁基锂 、 三甲基氯硅烷 作用下， 生成 N-trimethylsilylphenylpropargylideneimine
  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。
• Complete stereoselective synthesis of chiral intermediates for thienamycin and related antibiotics
  作者：Nobuki Oguni、Yohko Ohkawa

  DOI：10.1039/c39880001376

  日期：——

  The complete stereoselective synthesis of (3R,4R)-3-[(S)-1′-hydroxyethyl]-4-phenylethynyl-2-azetidinone and its 4-phenyethenyl derivative were accomplished by the reaction of the organozinc derivative of (R)-methyl-3-hydroxybutyrate with N-trimethylsilylimines.

  （3 R，4 R）-3-[（S）-1'-羟乙基] -4-苯基乙炔基-2-氮杂环丁酮及其4-苯乙烯基衍生物的完全立体选择性合成是通过（R）-3-羟基丁酸甲基酯与N-三甲基甲硅烷基亚胺。
• A new and efficient route to 3-amino-2-azetidinones via zinc enolates of N,N-disubstituted glycine esters
  作者：Fred H. Van der Steen、Henk Kleijn、Johann T. B. H. Jastrzebski、Gerard Van Koten

  DOI：10.1021/jo00017a030

  日期：1991.8

  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.
• Synthesis of NH -3-phenylsulfanyl- and NH -3-benzylsulfanyl-azetidinones from 1-phenylsulfanyl- or 1-benzylsulfanyl-3-aza-1,3-dienes
  作者：Mauro Panunzio、Alessandro Bongini、Emiliano Tamanini、Eileen Campana、Giorgio Martelli、Paola Vicennati、Ilaria Zanardi

  DOI：10.1016/j.tet.2003.10.004

  日期：2003.11

  The syntheses of NH-3-phenylsulfanyl- and NH-3-benzylsulfanyl-azetidinones, starting from 1-phenylsulfanyl- or 1-benzylsulfanyl-2-trimethylsilyloxy-3-aza-1,3-dienes are reported. (C) 2003 Elsevier Ltd. All rights reserved.
• KOKUNI, NOBUKI
  作者：KOKUNI, NOBUKI

  DOI：——

  日期：——