5,6-Dihydro-6-<(trimethylsilyl)methyl>-3-(trifluoromethyl)-4H-1,2-oxazine | 137496-15-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 5,6-Dihydro-6-<(trimethylsilyl)methyl>-3-(trifluoromethyl)-4H-1,2-oxazine
• 英文别名: 5,6-Dihydro-5-<(trimethylsilyl)methyl>-3-(trifluoromethyl)-4H-1,2-oxazine；(r,s)-3-Trifluoromethyl-6-trimethylsilanylmethyl-5,6-dihydro-4h-[1,2]oxazine；trimethyl-[[3-(trifluoromethyl)-5,6-dihydro-4H-oxazin-6-yl]methyl]silane
• CAS: 137496-15-2
• 化学式: C₉H₁₆F₃NOSi
• 分子量: 239.313
• InChiKey: CWCZEKCSMUSMJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.42
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5,6-Dihydro-6-<(trimethylsilyl)methyl>-3-(trifluoromethyl)-4H-1,2-oxazine 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以74%的产率得到2-Amino-1,1,1-trifluoro-6-(trimethylsilyl)hexan-5-ol
  参考文献：
  名称：

  Efficient synthesis of trifluoromethyl-substituted 5,6-dihydro-4H-1,2-oxazines by the hetero-Diels-Alder reaction of 1,1,1-trifluoro-2-nitroso-2-propene and electron-rich olefins

  摘要：

  1,1,1-Trifluoro-2-nitroso-2-propene (1) was generated in situ by treatment of the alpha-bromo oxime 5 with base. Moderate to excellent yields of the 3-trifluoromethyl-substituted 1,2-oxazines 17-27 were obtained from the reaction of 1 and the silyl enol ethers 6-16, respectively. Other dienophiles, i.e., allyltrimethylsilane, cyclopentadiene, furan, and dihydropyran, upon reaction with 1 provided the cycloadducts 31-34, respectively, in good yield. The results demonstrated that 1 is probably the most reactive heterodiene that has so far been employed in this type of Diels-Alder reaction (i.e., Diels-Alder reaction with inverse electron demand). The mechanism of the reaction and diastereoselectivity of the cycloadditions are discussed. The reaction of 1 with indole and acetyl acetone afforded the oxime 38 and a mixture of the isomers 40-42, respectively. Also, ring openings and other transformations of the trifluoromethyl-substituted 1,2-oxazines were effected. Acid-induced desilylation of the silylated 1,2-oxazines provided oximes like 46 and 48 or 6-hydroxy-1,2-oxazines like 47. Treatment of the 1,2-oxazines with Mo(CO)6 in the presence of trifluoroacetic acid produced 2-trifluoromethyl-substituted pyrroles (e.g., 18 --> 50). The reduction of the 1,2-oxazines afforded either gamma-hydroxy oximes (e.g., 19 --> 51) or amino alcohols (e.g., 32 --> 52, 31 --> 55). The reduction of the indole derivative 38 by LiAlH4 provided the trifluoromethyl-substituted tryptamine 56. The results of these explorative studies demonstrated that readily available trifluoromethyl-substituted 1,2-oxazines could be efficiently converted into other compounds that bear a trifluoromethyl group.

  DOI：

  10.1021/jo00027a058
• 作为产物：
  描述：

  3-bromo-1,1,1-trifluoropropan-2-one oxime 、 烯丙基三甲基硅烷 在 sodium carbonate 作用下， 以 various solvent(s) 为溶剂， 反应 120.0h， 以70%的产率得到5,6-Dihydro-6-<(trimethylsilyl)methyl>-3-(trifluoromethyl)-4H-1,2-oxazine
  参考文献：
  名称：

  Efficient synthesis of trifluoromethyl-substituted 5,6-dihydro-4H-1,2-oxazines by the hetero-Diels-Alder reaction of 1,1,1-trifluoro-2-nitroso-2-propene and electron-rich olefins

  摘要：

  1,1,1-Trifluoro-2-nitroso-2-propene (1) was generated in situ by treatment of the alpha-bromo oxime 5 with base. Moderate to excellent yields of the 3-trifluoromethyl-substituted 1,2-oxazines 17-27 were obtained from the reaction of 1 and the silyl enol ethers 6-16, respectively. Other dienophiles, i.e., allyltrimethylsilane, cyclopentadiene, furan, and dihydropyran, upon reaction with 1 provided the cycloadducts 31-34, respectively, in good yield. The results demonstrated that 1 is probably the most reactive heterodiene that has so far been employed in this type of Diels-Alder reaction (i.e., Diels-Alder reaction with inverse electron demand). The mechanism of the reaction and diastereoselectivity of the cycloadditions are discussed. The reaction of 1 with indole and acetyl acetone afforded the oxime 38 and a mixture of the isomers 40-42, respectively. Also, ring openings and other transformations of the trifluoromethyl-substituted 1,2-oxazines were effected. Acid-induced desilylation of the silylated 1,2-oxazines provided oximes like 46 and 48 or 6-hydroxy-1,2-oxazines like 47. Treatment of the 1,2-oxazines with Mo(CO)6 in the presence of trifluoroacetic acid produced 2-trifluoromethyl-substituted pyrroles (e.g., 18 --> 50). The reduction of the 1,2-oxazines afforded either gamma-hydroxy oximes (e.g., 19 --> 51) or amino alcohols (e.g., 32 --> 52, 31 --> 55). The reduction of the indole derivative 38 by LiAlH4 provided the trifluoromethyl-substituted tryptamine 56. The results of these explorative studies demonstrated that readily available trifluoromethyl-substituted 1,2-oxazines could be efficiently converted into other compounds that bear a trifluoromethyl group.

  DOI：

  10.1021/jo00027a058

文献信息

• Lithiated 3-trifluoromethyl-substituted 1,2-oxazines and their reactions
  作者：Reinhold Zimmer、Hans-Ulrich Reissig

  DOI：10.1016/s0022-1139(96)03454-9

  日期：1996.9

  3-Trifluoromethyl-substituted 1,2-oxazine 1 was smoothly deprotonated with lithiumdiisopropylamine and subsequently treated with various electrophiles. Reactions with alkyl halides furnished the 4-alkylated 1,2-oxazines 4-7 in good yield and with excellent cis-diastereoselectivity, whereas carbonyl compounds could not be employed successfully as electrophiles. Deuteration of lithiated 1 afforded the 4-deuterated product 2 as a single diastereomer. Transfer of a nitro group was achieved with isoamyl nitrate as electrophile. A structure for lithiated 1 is proposed to explain the high diastereoselectivities. Treatment of 1,2-oxazines 5-7 with HClO4 provided the trifluoromethyl-substituted oximes 11-13 in good yield, whereas reduction of 4 with LiAlH4 furnished 3,4,5,6-tetrahydro-2H-1,2-oxazine 14 with excellent diastereoselectivity.
• Efficient synthesis of trifluoromethyl-substituted 5,6-dihydro-4H-1,2-oxazines by the hetero-Diels-Alder reaction of 1,1,1-trifluoro-2-nitroso-2-propene and electron-rich olefins
  作者：Reinhold Zimmer、Hans Ulrich Reissig

  DOI：10.1021/jo00027a058

  日期：1992.1

  1,1,1-Trifluoro-2-nitroso-2-propene (1) was generated in situ by treatment of the alpha-bromo oxime 5 with base. Moderate to excellent yields of the 3-trifluoromethyl-substituted 1,2-oxazines 17-27 were obtained from the reaction of 1 and the silyl enol ethers 6-16, respectively. Other dienophiles, i.e., allyltrimethylsilane, cyclopentadiene, furan, and dihydropyran, upon reaction with 1 provided the cycloadducts 31-34, respectively, in good yield. The results demonstrated that 1 is probably the most reactive heterodiene that has so far been employed in this type of Diels-Alder reaction (i.e., Diels-Alder reaction with inverse electron demand). The mechanism of the reaction and diastereoselectivity of the cycloadditions are discussed. The reaction of 1 with indole and acetyl acetone afforded the oxime 38 and a mixture of the isomers 40-42, respectively. Also, ring openings and other transformations of the trifluoromethyl-substituted 1,2-oxazines were effected. Acid-induced desilylation of the silylated 1,2-oxazines provided oximes like 46 and 48 or 6-hydroxy-1,2-oxazines like 47. Treatment of the 1,2-oxazines with Mo(CO)6 in the presence of trifluoroacetic acid produced 2-trifluoromethyl-substituted pyrroles (e.g., 18 --> 50). The reduction of the 1,2-oxazines afforded either gamma-hydroxy oximes (e.g., 19 --> 51) or amino alcohols (e.g., 32 --> 52, 31 --> 55). The reduction of the indole derivative 38 by LiAlH4 provided the trifluoromethyl-substituted tryptamine 56. The results of these explorative studies demonstrated that readily available trifluoromethyl-substituted 1,2-oxazines could be efficiently converted into other compounds that bear a trifluoromethyl group.