6-[(4-methylphenyl)sulfonyl]-5,6-dihydro-2H-1,6-benzoxazocine

• 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: 6-[(4-methylphenyl)sulfonyl]-5,6-dihydro-2H-1,6-benzoxazocine
• 英文别名: (Z)-6-tosyl-5,6-dihydro-2H-benzo[b][1,4]oxazocine；(3Z)-6-(4-methylphenyl)sulfonyl-2,5-dihydro-1,6-benzoxazocine
• 化学式: C₁₇H₁₇NO₃S
• 分子量: 315.393
• InChiKey: XCICWMZUANTLSZ-PLNGDYQASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6-[(4-methylphenyl)sulfonyl]-5,6-dihydro-2H-1,6-benzoxazocine 在 2-[(S)-4-phenyl-2-oxazolyl]quinoline 、 palladium diacetate 、 对甲基苯甲酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以84%的产率得到(R)-4-tosyl-2-vinyl-3,4-dihydro-2H-benzo[b][1,4]oxazine
  参考文献：
  名称：

  Pd(II)-催化对映选择性环收缩用于构建 1,4-苯并恶嗪

  摘要：

  对映选择性环收缩反应尚未被广泛报道。我们开发了 5,6-dihydro-2 H -benzo [ b ][1,4]oxazocines 的对映选择性环收缩，提供对映体富集的 3,4-dihydro-2 H -1,4-benzoxazine衍生物作为单一区域异构体。为了获得具有良好产率和对映体比率（高达 93% 产率，98:2 er）的产品，酸性添加剂是必需的。该反应成功地进行了克级反应，产物易于衍生化。

  DOI：

  10.1021/acs.joc.1c01874
• 作为产物：
  描述：

  2-{[(4-methylphenyl)sulfonyl]amino}phenyl 4-meythylbenzenesulfonate 在 Grubbs' second generation catalyst C₃₀H₅₀Cl₂N₂O₄PS₂Ru potassium carbonate 、 magnesium 作用下， 以 甲醇 、 丙酮 、 甲苯 为溶剂， 反应 31.0h， 生成 6-[(4-methylphenyl)sulfonyl]-5,6-dihydro-2H-1,6-benzoxazocine
  参考文献：
  名称：

  Isomerization and ring-closing metathesis for the synthesis of 6-, 7- and 8-membered benzo- and pyrido-fused N,N-, N,O- and N,S-heterocycles

  摘要：

  An isomerization-ring-closing metathesis (RCM) strategy afforded N-substituted 4H-1,4-benzoxazines from the protected N-allyl-2-(allyloxy)anilines. In addition, RCM was used to synthesize the N-substituted, 8-membered benzo-fused heterocycles from the respective diallyl compounds: 1,2,5,6-tetraliydro-1,6-benzodiazocine, 5,6-dihydro-2H-1,6-benzoxazocine, 5,6,9, 10-tetrahydropyrido[2,3-b][1,4]diazocine and 5,6-dihydro-2H-1,6-benzothiazocine 1,1-dioxide. The isomerization-RCM approach also afforded the 7-membered ring system, 2,5-diliydro-1,5-benzothiazepine 1,1-dioxide, from the protected N-allyl-2-(allylsulfonyl)aniline. Furthermore, the structure of 1,6-bis[(4-methylplienyl)sulfonyl]-1,2,5,6-tetrahydro-1,6-benzodiazocine was confirmed by a single crystal X-ray determination. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.10.108

文献信息

• A ring-closing metathesis approach to eight-membered benzannelated scaffolds and subsequent internal alkene isomerizations
  作者：Abu Taher、Blessing A. Aderibigbe、Garreth L. Morgans、Lee G. Madeley、Setshaba D. Khanye、Leandi van der Westhuizen、Manuel A. Fernandes、Vincent J. Smith、Joseph P. Michael、Ivan R. Green、Willem A.L. van Otterlo

  DOI：10.1016/j.tet.2012.12.043

  日期：2013.2

  A set of eight-membered benzannelated heterocycles containing two heteroatoms (O,O, NR,NR and O,NR where R=protecting group) was synthesized by ring-closing metathesis from the corresponding orthobis-allyl precursors. In this manner, 7-methoxy-2,5-dihydro-1,6-benzodioxocine, 1,2,5,6-tetrahydro-1,6-benzodiazocines, 5,6-dihydro-2H-1,6-benzoxazocines and 5,6,9,10-tetrahydropyrido[2,3-b][1,4]diazocine were synthesized. A number of these compounds were then treated with the catalyst [RuClH(CO)(PPh3)(3)] to facilitate isomerization of the alkene into conjugation with the heteroatoms in the eight-membered ring. Quite surprisingly, an equal ratio of regioisomers was obtained, even if the heteroatoms were different (c) 2012 Elsevier Ltd. All rights reserved.
• Isomerization and ring-closing metathesis for the synthesis of 6-, 7- and 8-membered benzo- and pyrido-fused N,N-, N,O- and N,S-heterocycles
  作者：Willem A.L. van Otterlo、Garreth L. Morgans、Setshaba D. Khanye、Blessing A.A. Aderibigbe、Joseph P. Michael、David G. Billing

  DOI：10.1016/j.tetlet.2004.10.108

  日期：2004.12

  An isomerization-ring-closing metathesis (RCM) strategy afforded N-substituted 4H-1,4-benzoxazines from the protected N-allyl-2-(allyloxy)anilines. In addition, RCM was used to synthesize the N-substituted, 8-membered benzo-fused heterocycles from the respective diallyl compounds: 1,2,5,6-tetraliydro-1,6-benzodiazocine, 5,6-dihydro-2H-1,6-benzoxazocine, 5,6,9, 10-tetrahydropyrido[2,3-b][1,4]diazocine and 5,6-dihydro-2H-1,6-benzothiazocine 1,1-dioxide. The isomerization-RCM approach also afforded the 7-membered ring system, 2,5-diliydro-1,5-benzothiazepine 1,1-dioxide, from the protected N-allyl-2-(allylsulfonyl)aniline. Furthermore, the structure of 1,6-bis[(4-methylplienyl)sulfonyl]-1,2,5,6-tetrahydro-1,6-benzodiazocine was confirmed by a single crystal X-ray determination. (C) 2004 Elsevier Ltd. All rights reserved.
• Pd(II)-Catalyzed Enantioselective Ring-Contraction for the Construction of 1,4-Benzoxazines
  作者：Chenghao Ye、Feng Gao、Haipeng Wei、Jianzhong Chen、Guoqiang Yang、Qianjia Yuan、Wanbin Zhang

  DOI：10.1021/acs.joc.1c01874

  日期：2021.12.3

  Enantioselective ring-contraction reactions have not been widely reported. We have developed an enantioselective ring contraction of 5,6-dihydro-2H-benzo[b][1,4]oxazocines, affording enantiomerically enriched 3,4-dihydro-2H-1,4-benzoxazine derivatives as single regioisomers. An acidic additive is necessary in order to obtain the products with good yields and enantiomeric ratios (up to 93% yield, 98:2

  对映选择性环收缩反应尚未被广泛报道。我们开发了 5,6-dihydro-2 H -benzo [ b ][1,4]oxazocines 的对映选择性环收缩，提供对映体富集的 3,4-dihydro-2 H -1,4-benzoxazine衍生物作为单一区域异构体。为了获得具有良好产率和对映体比率（高达 93% 产率，98:2 er）的产品，酸性添加剂是必需的。该反应成功地进行了克级反应，产物易于衍生化。