N-<(R)-1-Phenylethyl>-N-tigloylthiobenzamide | 155512-53-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-<(R)-1-Phenylethyl>-N-tigloylthiobenzamide
• 英文别名: (E)-N-(benzenecarbonothioyl)-2-methyl-N-[(1R)-1-phenylethyl]but-2-enamide
• CAS: 155512-53-1
• 化学式: C₂₀H₂₁NOS
• 分子量: 323.459
• InChiKey: UYUUNGPQCMNACR-UDCCBSLUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  52.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-<(R)-1-Phenylethyl>-N-tigloylthiobenzamide 反应 0.08h， 生成 4,5-Dimethyl-1-phenyl-2-<(R)-1-phenylethyl>-6-thia-2-azabicyclo<2.2.0>hexan-3-one 、 (1R,4R,5S)-4,5-Dimethyl-1-phenyl-2-<(R)-1-phenylethyl>-6-thia-2-azabicyclo<2.2.0>hexan-3-one
  参考文献：
  名称：

  Solid-State Photochemistry: Diastereoselective Synthesis of Thietane-Fused .beta.-Lactams from an Acyclic Monothioimide with a Chiral Group

  摘要：

  Irradiation of N-[(R)-1-phenylethyl]-N-tigloythiobenzamide in benzene solution resulted in both [2 + 2] thietane and thioketone formation reactions (via beta-hydrogen abstraction by the thiocarbonyl sulfur). Diastereoselectivity in the thietane formation was not observed, in that four beta-lactams were obtained in similar yields. In contrast to the solution photochemistry, irradiation of the crystals provided remarkably high diastereoselectivities. At 15 degrees C, de of the syn-beta-lactams was 61% and the ratio of syn/anti was to 8.7 (chemical yield: 78%). The solid-state photoreaction proceeded even at -78 degrees C, with higher diastereoselectivity. At low conversion (9%), only syn isomers (de = 93%) were obtained, and 71% de was observed even at 90% conversion. An X-ray crystal structure analysis of the monothioimide indicates that the crystal is orthorhombic, of space group P2(1)2(1)2(1), and the distances between the sulfur atom and the alkenyl carbon, and from the thiocarbonyl carbon to the alkenyl carbon, are 4.29 and 3.00 Angstrom, respectively. The twist angle tau of the C(=O)-N bond is 40.8 degrees and that of the C(=S)-N bond is 19.9 degrees. On the other hand, the sulfur atom and abstractable hydrogen atom are in close proximity, and the value for d is 2.40 Angstrom, for theta is 127.3 degrees, for Delta is 67.9 degrees, and for omega is 6.2 degrees. From these values, it is apparent that this reactant is well-positioned for hydrogen transfer in the crystalline state.

  DOI：

  10.1021/jo00090a034
• 作为产物：
  描述：

  (E)-2-甲基-2-丁烯酰氯 、 N-<(R)-1-phenethyl>thiobenzamide 在 三乙胺 作用下， 以 苯 为溶剂， 反应 2.0h， 以93%的产率得到N-<(R)-1-Phenylethyl>-N-tigloylthiobenzamide
  参考文献：
  名称：

  Solid-State Photochemistry: Diastereoselective Synthesis of Thietane-Fused .beta.-Lactams from an Acyclic Monothioimide with a Chiral Group

  摘要：

  Irradiation of N-[(R)-1-phenylethyl]-N-tigloythiobenzamide in benzene solution resulted in both [2 + 2] thietane and thioketone formation reactions (via beta-hydrogen abstraction by the thiocarbonyl sulfur). Diastereoselectivity in the thietane formation was not observed, in that four beta-lactams were obtained in similar yields. In contrast to the solution photochemistry, irradiation of the crystals provided remarkably high diastereoselectivities. At 15 degrees C, de of the syn-beta-lactams was 61% and the ratio of syn/anti was to 8.7 (chemical yield: 78%). The solid-state photoreaction proceeded even at -78 degrees C, with higher diastereoselectivity. At low conversion (9%), only syn isomers (de = 93%) were obtained, and 71% de was observed even at 90% conversion. An X-ray crystal structure analysis of the monothioimide indicates that the crystal is orthorhombic, of space group P2(1)2(1)2(1), and the distances between the sulfur atom and the alkenyl carbon, and from the thiocarbonyl carbon to the alkenyl carbon, are 4.29 and 3.00 Angstrom, respectively. The twist angle tau of the C(=O)-N bond is 40.8 degrees and that of the C(=S)-N bond is 19.9 degrees. On the other hand, the sulfur atom and abstractable hydrogen atom are in close proximity, and the value for d is 2.40 Angstrom, for theta is 127.3 degrees, for Delta is 67.9 degrees, and for omega is 6.2 degrees. From these values, it is apparent that this reactant is well-positioned for hydrogen transfer in the crystalline state.

  DOI：

  10.1021/jo00090a034

文献信息

• Solid-State Photochemistry: Diastereoselective Synthesis of Thietane-Fused .beta.-Lactams from an Acyclic Monothioimide with a Chiral Group
  作者：Masami Sakamoto、Masaki Takahashi、Noriko Hokari、Tsutomu Fujita、Shoji Watanabe

  DOI：10.1021/jo00090a034

  日期：1994.6

  Irradiation of N-[(R)-1-phenylethyl]-N-tigloythiobenzamide in benzene solution resulted in both [2 + 2] thietane and thioketone formation reactions (via beta-hydrogen abstraction by the thiocarbonyl sulfur). Diastereoselectivity in the thietane formation was not observed, in that four beta-lactams were obtained in similar yields. In contrast to the solution photochemistry, irradiation of the crystals provided remarkably high diastereoselectivities. At 15 degrees C, de of the syn-beta-lactams was 61% and the ratio of syn/anti was to 8.7 (chemical yield: 78%). The solid-state photoreaction proceeded even at -78 degrees C, with higher diastereoselectivity. At low conversion (9%), only syn isomers (de = 93%) were obtained, and 71% de was observed even at 90% conversion. An X-ray crystal structure analysis of the monothioimide indicates that the crystal is orthorhombic, of space group P2(1)2(1)2(1), and the distances between the sulfur atom and the alkenyl carbon, and from the thiocarbonyl carbon to the alkenyl carbon, are 4.29 and 3.00 Angstrom, respectively. The twist angle tau of the C(=O)-N bond is 40.8 degrees and that of the C(=S)-N bond is 19.9 degrees. On the other hand, the sulfur atom and abstractable hydrogen atom are in close proximity, and the value for d is 2.40 Angstrom, for theta is 127.3 degrees, for Delta is 67.9 degrees, and for omega is 6.2 degrees. From these values, it is apparent that this reactant is well-positioned for hydrogen transfer in the crystalline state.