2,2-dimethyl-5-trimethylsilyloxy-4-aza-3,5-heptadiene | 172095-52-2

• 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: 2,2-dimethyl-5-trimethylsilyloxy-4-aza-3,5-heptadiene
• 英文别名: (E)-2,2-dimethyl-N-[(Z)-1-trimethylsilyloxyprop-1-enyl]propan-1-imine
• CAS: 172095-52-2
• 化学式: C₁₁H₂₃NOSi
• 分子量: 213.395
• InChiKey: SCSSTCDVTFCLHO-XXBUAHSKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.82
• 重原子数：
  14
• 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：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-5-trimethylsilyloxy-4-aza-3,5-heptadiene 、 alkaline earth salt of/the/ methylsulfuric acid 以 四氢呋喃 为溶剂， 反应 18.0h， 以62%的产率得到(1R,4S,9S)-1-tert-Butyl-9-methoxy-4-methyl-1,2,4,9-tetrahydro-indeno[2,1-c]pyridin-3-one
  参考文献：
  名称：

  Fischer Carbene Complexes in Heterocyclic Synthesis. Selective Cycloaddition Reactions to 2-Aza-1,3-butadienes

  摘要：

  A structurally diverse set of Fischer carbene complexes are reacted with substituted 3-[(trimethylsilyl)oxy]-2-aza-1,3-butadienes 1, yielding 5- to 7-membered nitrogen-containing heterocycles in a selective manner. Aryl and heteroarylmetal carbenes 2 undergo [4 + 1] cycloaddition with 1 leading to pyrrolidone derivatives 3-5 or 6-9, depending on the C1-substituent of 1. The [(trimethylsilyl)ethynyl]carbene 10a gives rise to metal-containing and metal-free [4 + 2] cycloadducts 11 and 12, respectively, whereas the (phenylethynyl)carbene 10b furnishes azafluorenones 13 by a tandem [4 + 2] cycloaddition/pentaannulation process. In the case of alkenyl carbene complexes 14 the regioselective [4 + 3] cycloaddition is the only observed transformation. Thus, their reaction with the phenyl-substituted azadiene 1d-resulted in the formation of a approximate to 1:1 mixture of diastereoisomers 15 and 16, whereas in the case of the tert-butyl-substituted azadiene Ic the cis-diastereoisomers 15 are selectively formed. This heptaannulation is proposed to occur by a cyclopropanation/aza-Cope rearrangement.

  DOI：

  10.1021/jo9715074
• 作为产物：
  描述：

  丙酰氯 、 N-trimethylsilyl-2,2-dimethylpropionaldimine 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以66%的产率得到2,2-dimethyl-5-trimethylsilyloxy-4-aza-3,5-heptadiene
  参考文献：
  名称：

  2-氮杂-1,3-二烯：合成方法和立体化学研究

  摘要：

  已经通过三种途径制备了在C-3处带有活化三烷基甲硅烷基氧基的2-Aza-1，3-二烯。第一条途径涉及N-酰基酰亚胺的甲硅烷基化，其可从亚氨基醚盐酸盐和酰氯容易获得。根据朝向这些双活化二烯的更通用的途径，通过在三乙胺的存在下与酰氯反应，将由不可烯化的醛衍生的N-三烷基甲硅烷基酰亚胺酯和N-三烷基甲硅烷基亚胺方便地以一锅法转化为相应的氮杂二烯。最后，可以通过在三乙胺的存在下用三烷基甲硅烷基三氟甲磺酸酯在两个氧上将戊二酰亚胺直接甲硅烷基化来制备环状二烯。2-氮二烯的构型和构象已由1 H，13确定C和15 N NMR光谱。

  DOI：

  10.1016/0040-4020(95)00657-t

文献信息

• Diastereoselective β-Hydroxyalkylation and β-Hydroxycarboxylation of Amides­ by a Diels-Alder Strategy
  作者：Léon Ghosez、Deogratias Ntirampebura

  DOI：10.1055/s-2002-34367

  日期：——

  Acid chlorides readily condensed with N-silylated imines in the presence of a base to generate 2-azadienes. These underwent Diels-Alder cycloadditions with a wide variety of aldehydes.. In most cases the cycloadditions were diastereoselective in favor of the 3,4-cis-oxazinone adducts. Ethanolysis stereoselectively yielded products of hydroxyalkylation or hydroxycarboxylation of the primary amides derived

  在碱的存在下，酰氯很容易与 N-甲硅烷基化亚胺缩合生成 2-氮杂二烯。这些经历了与多种醛的 Diels-Alder 环加成反应。在大多数情况下，环加成反应是非对映选择性的，有利于 3,4-顺式-恶嗪酮加合物。乙醇解立体选择性地产生衍生自初始酰氯的伯酰胺的羟烷基化或羟羧化产物。
• 2-aza-1,3-dienes: Methods of synthesis and stereochemical studies
  作者：L. Ghosez、Ph. Bayard、P. Nshimyumukiza、V. Gouverneur、F. Sainte、R. Beaudegnies、M. Rivera、A.-M. Frisque-Hesbain、C. Wynants

  DOI：10.1016/0040-4020(95)00657-t

  日期：1995.10

  readily available from iminoether hydrochlorides and acid chlorides. According to a more general route towards these doubly activated dienes, N-trialkylsilylimidates and N-trialkylsilylimines derived from non-enolizable aldehydes were conveniently converted in a one-pot sequence into the corresponding azadienes by reaction with an acid chloride in the presence of triethylamine. Finally, cyclic dienes could

  已经通过三种途径制备了在C-3处带有活化三烷基甲硅烷基氧基的2-Aza-1，3-二烯。第一条途径涉及N-酰基酰亚胺的甲硅烷基化，其可从亚氨基醚盐酸盐和酰氯容易获得。根据朝向这些双活化二烯的更通用的途径，通过在三乙胺的存在下与酰氯反应，将由不可烯化的醛衍生的N-三烷基甲硅烷基酰亚胺酯和N-三烷基甲硅烷基亚胺方便地以一锅法转化为相应的氮杂二烯。最后，可以通过在三乙胺的存在下用三烷基甲硅烷基三氟甲磺酸酯在两个氧上将戊二酰亚胺直接甲硅烷基化来制备环状二烯。2-氮二烯的构型和构象已由1 H，13确定C和15 N NMR光谱。
• Fischer Carbene Complexes in Heterocyclic Synthesis. Selective Cycloaddition Reactions to 2-Aza-1,3-butadienes
  作者：José Barluenga、Miguel Tomás、Alfredo Ballesteros、Javier Santamaría、Angel Suárez-Sobrino

  DOI：10.1021/jo9715074

  日期：1997.12.1

  A structurally diverse set of Fischer carbene complexes are reacted with substituted 3-[(trimethylsilyl)oxy]-2-aza-1,3-butadienes 1, yielding 5- to 7-membered nitrogen-containing heterocycles in a selective manner. Aryl and heteroarylmetal carbenes 2 undergo [4 + 1] cycloaddition with 1 leading to pyrrolidone derivatives 3-5 or 6-9, depending on the C1-substituent of 1. The [(trimethylsilyl)ethynyl]carbene 10a gives rise to metal-containing and metal-free [4 + 2] cycloadducts 11 and 12, respectively, whereas the (phenylethynyl)carbene 10b furnishes azafluorenones 13 by a tandem [4 + 2] cycloaddition/pentaannulation process. In the case of alkenyl carbene complexes 14 the regioselective [4 + 3] cycloaddition is the only observed transformation. Thus, their reaction with the phenyl-substituted azadiene 1d-resulted in the formation of a approximate to 1:1 mixture of diastereoisomers 15 and 16, whereas in the case of the tert-butyl-substituted azadiene Ic the cis-diastereoisomers 15 are selectively formed. This heptaannulation is proposed to occur by a cyclopropanation/aza-Cope rearrangement.