5,6-dihydro-6-methyl-4-phenyl-6-trimethylsilyloxy-4H-[1,2]oxazine 2-oxide | 308289-03-4

• 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: 5,6-dihydro-6-methyl-4-phenyl-6-trimethylsilyloxy-4H-[1,2]oxazine 2-oxide
• 英文别名: Trimethyl-[(6-methyl-2-oxido-4-phenyl-4,5-dihydrooxazin-2-ium-6-yl)oxy]silane
• CAS: 308289-03-4
• 化学式: C₁₄H₂₁NO₃Si
• 分子量: 279.411
• InChiKey: JNFVDBCZCAQZDQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  47.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,6-dihydro-6-methyl-4-phenyl-6-trimethylsilyloxy-4H-[1,2]oxazine 2-oxide 在 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 2-phenylpropenal oxime
  参考文献：
  名称：

  Novel Me3Si-Mediated Intramolecular Cyclisation/[4 + 2] Cyclofragmentation of β-Substituted γ-Nitro Ketones

  摘要：

  5-Nitro-4-phenylpentan-2-one (1) was found to undergo hitherto unknown Me3SiBr/Et3N-promoted cyclisation into the intermediate six-membered cyclic nitronate 5. Subsequent silylation of 5 led to the corresponding 2-trimethylsilyloxy-2H-[1,2]oxazine C, which undergoes a facile [4 + 2] cyclofragmentation to give 2-phenylpropenal oxime trimethylsilyl ether (6) in moderate yield. The intermediacy of the open-chain trimethylsilyl nitronate 2 and the cyclic nitronate 5 was confirmed by independent experiments. The transformation of the bicyclic nitronate 8 into the 8-trimethylsilyl-oxyimino-7-phenyloct-6-enoic acid trimethylsilyl ester (9) upon silylation proved the silylation/cycloreversion to be a key step in 1,3-azadiene moiety formation. The presented sequence of reactions could be carried out in one pot in low yield by a Me3SiOTf/Et3N-promoted hetero-[4 + 2] cycloaddition of 2-(trimethylsilyloxy)propene to (E)-2-nitro-1-phenyl-ethene, followed by silylation and fragmentation of the intermediate C.

  DOI：

  10.1002/1099-0690(200009)2000:18<3229::aid-ejoc3229>3.0.co;2-m
• 作为产物：
  描述：

  反式硝基苯乙烯 、 2-(三甲基硅氧基)丙烯 在 二异丙氧基二氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以91%的产率得到5,6-dihydro-6-methyl-4-phenyl-6-trimethylsilyloxy-4H-[1,2]oxazine 2-oxide
  参考文献：
  名称：

  Novel Me3Si-Mediated Intramolecular Cyclisation/[4 + 2] Cyclofragmentation of β-Substituted γ-Nitro Ketones

  摘要：

  5-Nitro-4-phenylpentan-2-one (1) was found to undergo hitherto unknown Me3SiBr/Et3N-promoted cyclisation into the intermediate six-membered cyclic nitronate 5. Subsequent silylation of 5 led to the corresponding 2-trimethylsilyloxy-2H-[1,2]oxazine C, which undergoes a facile [4 + 2] cyclofragmentation to give 2-phenylpropenal oxime trimethylsilyl ether (6) in moderate yield. The intermediacy of the open-chain trimethylsilyl nitronate 2 and the cyclic nitronate 5 was confirmed by independent experiments. The transformation of the bicyclic nitronate 8 into the 8-trimethylsilyl-oxyimino-7-phenyloct-6-enoic acid trimethylsilyl ester (9) upon silylation proved the silylation/cycloreversion to be a key step in 1,3-azadiene moiety formation. The presented sequence of reactions could be carried out in one pot in low yield by a Me3SiOTf/Et3N-promoted hetero-[4 + 2] cycloaddition of 2-(trimethylsilyloxy)propene to (E)-2-nitro-1-phenyl-ethene, followed by silylation and fragmentation of the intermediate C.

  DOI：

  10.1002/1099-0690(200009)2000:18<3229::aid-ejoc3229>3.0.co;2-m

文献信息

• Novel Me3Si-Mediated Intramolecular Cyclisation/[4 + 2] Cyclofragmentation of β-Substituted γ-Nitro Ketones
  作者：Alexander A. Tishkov、Il’ya M. Lyapkalo、Anton V. Kozincev、Sema L. Ioffe、Yuri A. Strelenko、Vladimir A. Tartakovsky

  DOI：10.1002/1099-0690(200009)2000:18<3229::aid-ejoc3229>3.0.co;2-m

  日期：2000.9

  5-Nitro-4-phenylpentan-2-one (1) was found to undergo hitherto unknown Me3SiBr/Et3N-promoted cyclisation into the intermediate six-membered cyclic nitronate 5. Subsequent silylation of 5 led to the corresponding 2-trimethylsilyloxy-2H-[1,2]oxazine C, which undergoes a facile [4 + 2] cyclofragmentation to give 2-phenylpropenal oxime trimethylsilyl ether (6) in moderate yield. The intermediacy of the open-chain trimethylsilyl nitronate 2 and the cyclic nitronate 5 was confirmed by independent experiments. The transformation of the bicyclic nitronate 8 into the 8-trimethylsilyl-oxyimino-7-phenyloct-6-enoic acid trimethylsilyl ester (9) upon silylation proved the silylation/cycloreversion to be a key step in 1,3-azadiene moiety formation. The presented sequence of reactions could be carried out in one pot in low yield by a Me3SiOTf/Et3N-promoted hetero-[4 + 2] cycloaddition of 2-(trimethylsilyloxy)propene to (E)-2-nitro-1-phenyl-ethene, followed by silylation and fragmentation of the intermediate C.