(4RS,6RS)-6-methyloxy-6-methyl-2-trimethylsilyloxy-3-methylidene-4-phenyl-2,3,5,6-tetrahydro-1,2-oxazine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: (4RS,6RS)-6-methyloxy-6-methyl-2-trimethylsilyloxy-3-methylidene-4-phenyl-2,3,5,6-tetrahydro-1,2-oxazine
• 英文别名: [(4R,6R)-6-methoxy-6-methyl-3-methylidene-4-phenyloxazinan-2-yl]oxy-trimethylsilane
• 化学式: C₁₆H₂₅NO₃Si
• 分子量: 307.465
• InChiKey: WILXBWPPCCWSAD-JKSUJKDBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  30.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4RS,6RS)-6-methyloxy-6-methyl-2-trimethylsilyloxy-3-methylidene-4-phenyl-2,3,5,6-tetrahydro-1,2-oxazine 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以22%的产率得到3-(methoxymethyl)-6-methyl-4-phenyl-6-(trimethylsilyloxy)-5,6-dihydro-4H-1,2-oxazine
  参考文献：
  名称：

  Rearrangement of 3-alkylidene-2-siloxy-tetrahydro-1,2-oxazines (ASENA). A new approach toward the synthesis of 3-α-hydroxyalkyl-5,6-dihydro-4H-1,2-oxazines

  摘要：

  A new approach toward the synthesis of 3-alpha-hydroxyalkyl-5,6-dihydro-4H-1,2-oxazines 1 from available 5,6-dihydro-4H-1,2-oxazine N-oxides 2 has been described. The key step of the process-the rearrangement of 3-alkiliden-2-siloxy-tetrahydro-1,2-oxazines 3 (ASENA)-was thoroughly investigated. Optimal experimental conditions were developed. A possible pathway of the ASENA rearrangement was proposed. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.03.082
• 作为产物：
  描述：

  苯,(2-硝基-1-丙烯基)-,(E)- 在 四氯化锡 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.16h， 生成 (4RS,6RS)-6-methyloxy-6-methyl-2-trimethylsilyloxy-3-methylidene-4-phenyl-2,3,5,6-tetrahydro-1,2-oxazine
  参考文献：
  名称：

  2-甲硅烷氧基-1,2-恶嗪，一种新型的共轭亚硝基烯烃缩醛。

  摘要：

  用甲硅烷基化试剂处理后，可以将3-烷基取代的1，2-恶嗪N-氧化物2选择性地转化为2-甲硅烷氧基-1，2-恶嗪1。在固态衍生物1中，其构型与锥体氮原子呈椅构型，而在溶液中，它们呈两个构象体（DeltaG ++ 55-60 kJ / mol）的平衡混合物形式存在。对亚硝基化合物1的反应性的初步研究表明，它们与O和N稳定的碳阳离子反应，生成在3位带有官能化烷基取代基的1,2-恶嗪N-氧化物。此外，化合物1可以重排为甲硅烷氧基-1,2-恶嗪5，并与吗啉反应生成3-吗啉代烷基-1,2-恶嗪7，其与开链肟6以tautameric平衡存在。

  DOI：

  10.1021/jo034669a

文献信息

• 3-Halomethylated cyclic nitronates: synthesis and nucleophilic substitution
  作者：Andrey A. Mikhaylov、Alexander D. Dilman、Marina I. Struchkova、Yulia A. Khomutova、Alexander A. Korlyukov、Sema L. Ioffe、Vladimir A. Tartakovsky

  DOI：10.1016/j.tet.2011.04.078

  日期：2011.6

  group attached to the C-3 atom of five- and six-membered cyclic nitronates (isoxazoline N-oxides and oxazine N-oxides, respectively) has been studied. The process involves silylation of starting 3-methyl-substituted cyclic nitronates followed by halogenation of the resulting N-(silyloxy)enamines. While five- and six-membered cyclic enamines behave similarly toward elemental bromine and iodine, their

  已经研究了将卤素原子引入与五元和六元环状硝酸盐（分别为异恶唑啉N-氧化物和恶嗪N-氧化物）的C-3原子相连的甲基中的方法。该方法包括将起始的3-甲基取代的环状硝酸酯甲硅烷基化，然后将所得的N-（甲硅烷氧基）烯胺卤化。尽管五元和六元环状烯胺对元素溴和碘的行为相似，但它们与NBS的反应产生了不同的产物，这些产物通过立体电子效应得以合理化。将获得的卤代硝酸盐与各种亲核试剂偶联，得到在C-3位官能化的新的硝酸盐。
• Reaction of N,N-Dioxyenamines with Anhydrides of Carboxylic and Sulfonic Acids; A New Method for the Synthesis of α-Hydroxyoxime Derivatives
  作者：Alexey Lesiv、Andrey Tabolin、Sema Ioffe

  DOI：10.1055/s-0029-1216907

  日期：2009.9

  The reactions of N,N-dioxyenamines with carboxylic and sulfonic acid anhydrides were investigated. A new method for the synthesis of α-hydroxyoxime derivatives via the reaction of N,N-dioxyenamines with trifluoroacetic anhydride is described. 1,2-oxazine - trifluoroacetic anhydride - hydroxyoxime - enamine - rearrangement

  研究了N，N-二氧化烯胺与羧酸酐和磺酸酐的反应。描述了一种通过N，N-二氧化烯胺与三氟乙酸酐反应合成α-羟基肟衍生物的新方法。 1,2-恶嗪-三氟乙酸酐-羟基肟-烯胺-重排
• Klenov, Michael S.; Lesiv, Alexey V.; Khomutova, Yulya A., Synthesis, 2004, # 8, p. 1159 - 1170
  作者：Klenov, Michael S.、Lesiv, Alexey V.、Khomutova, Yulya A.、Nesterov, Ivan D.、Ioffe, Sema L.

  DOI：——

  日期：——
• Rearrangement of 3-alkylidene-2-siloxy-tetrahydro-1,2-oxazines (ASENA). A new approach toward the synthesis of 3-α-hydroxyalkyl-5,6-dihydro-4H-1,2-oxazines
  作者：Andrey A. Tabolin、Alexey V. Lesiv、Yulia A. Khomutova、Yulia V. Nelyubina、Sema L. Ioffe

  DOI：10.1016/j.tet.2009.03.082

  日期：2009.6

  A new approach toward the synthesis of 3-alpha-hydroxyalkyl-5,6-dihydro-4H-1,2-oxazines 1 from available 5,6-dihydro-4H-1,2-oxazine N-oxides 2 has been described. The key step of the process-the rearrangement of 3-alkiliden-2-siloxy-tetrahydro-1,2-oxazines 3 (ASENA)-was thoroughly investigated. Optimal experimental conditions were developed. A possible pathway of the ASENA rearrangement was proposed. (C) 2009 Elsevier Ltd. All rights reserved.
• 2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes
  作者：Alexander A. Tishkov、Alexey V. Lesiv、Yulya A. Khomutova、Yury A. Strelenko、Ivan D. Nesterov、Michael Yu. Antipin、Sema L. Ioffe、Scott E. Denmark

  DOI：10.1021/jo034669a

  日期：2003.11.1

  3-alkyl-substituted 1,2-oxazine N-oxides 2 can be selectively transformed into 2-silyloxy-1,2-oxazines 1 upon treatment with silylating reagents. In the solid state derivatives 1 adopt a chair conformation with the pyramidal nitrogen atom, whereas in solution they exist as an equilibrating mixture of two conformers (DeltaG++ 55-60 kJ/mol). A preliminary study of the reactivity of nitrosals 1 has shown

  用甲硅烷基化试剂处理后，可以将3-烷基取代的1，2-恶嗪N-氧化物2选择性地转化为2-甲硅烷氧基-1，2-恶嗪1。在固态衍生物1中，其构型与锥体氮原子呈椅构型，而在溶液中，它们呈两个构象体（DeltaG ++ 55-60 kJ / mol）的平衡混合物形式存在。对亚硝基化合物1的反应性的初步研究表明，它们与O和N稳定的碳阳离子反应，生成在3位带有官能化烷基取代基的1,2-恶嗪N-氧化物。此外，化合物1可以重排为甲硅烷氧基-1,2-恶嗪5，并与吗啉反应生成3-吗啉代烷基-1,2-恶嗪7，其与开链肟6以tautameric平衡存在。