(2R,3S,6R,7S)-methyl 6-bromo-2,7-dimethyl-4-((4-nitrophenyl)sulfonyl)-1,4-oxazepane-3-carboxylate | 1421070-64-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2R,3S,6R,7S)-methyl 6-bromo-2,7-dimethyl-4-((4-nitrophenyl)sulfonyl)-1,4-oxazepane-3-carboxylate
• 英文别名: methyl (2R,3S,6R,7S)-6-bromo-2,7-dimethyl-4-(4-nitrophenyl)sulfonyl-1,4-oxazepane-3-carboxylate
• CAS: 1421070-64-5
• 化学式: C₁₅H₁₉BrN₂O₇S
• 分子量: 451.295
• InChiKey: WCGDOJHMEDLVCS-PJQZNRQZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  127
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,3S,6R,7S)-methyl 6-bromo-2,7-dimethyl-4-((4-nitrophenyl)sulfonyl)-1,4-oxazepane-3-carboxylate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以22%的产率得到(2S,3R,5S)-methyl 3,5-dimethyl-2-(4-nitrophenyl)-4-oxa-1-azabicyclo[4.1.0]heptane-2-carboxylate
  参考文献：
  名称：

  氟化物介导的脱磺酰基分子内环化成稠合和桥联的双环化合物：复杂的机制。

  摘要：

  我们先前报道了由市售起始原料分三步合成多取代的手性恶唑烷。这些1，4-恶唑酮之一在TBAF存在下的意外反应提供了4-oxa-1-氮杂双环[4.1.0]庚烷核。这种不寻常的过程通过引入双环核心显着增加了分子支架的复杂性。出人意料的是，生成的具有三个立体中心的双环结构是对映异构体的混合物，未观察到其他非对映异构体。这些惊人的实验观察值得进一步研究。实验和计算研究相结合，揭示了一种复杂的非对映选择性机制。为观察到的这种重排提供了机械原理。

  DOI：

  10.1021/acs.joc.6b02999
• 作为产物：
  描述：

  (2S,3R)-methyl 2-(N-((E)-but-2-en-1-yl)-4-nitrophenylsulfonamido)-3-hydroxybutanoate 在 N-溴代丁二酰亚胺(NBS) 、 D(+)-10-樟脑磺酸 作用下， 以 四氢呋喃 为溶剂， 反应 17.0h， 以66%的产率得到(2R,3S,6R,7S)-methyl 6-bromo-2,7-dimethyl-4-((4-nitrophenyl)sulfonyl)-1,4-oxazepane-3-carboxylate
  参考文献：
  名称：

  Stereo- and Regioselective Synthesis of Polysubstituted Chiral 1,4-Oxazepanes

  摘要：

  The number of cyclic molecular scaffolds available to medicinal chemists remains limited, and simple structures such as oxazepanes are still made using multistep procedures, including a number of protection/deprotection steps and purifications. We report herein an expedient and efficient synthesis of chiral polysubstituted oxazepanes. The developed method relies on a regio- and stereoselective 7-endo cyclization through haloetherification. Mechanistic studies using a combination of computations and experiments confirmed the expected role of the asymmetry of the chiral bromonium intermediate on the haloetherification regioselectivity. Computations also suggested that the bromonium intermediate is formed with no transition state; hence, the stereoselectivity is controlled primarily by the conformation of the substrate. Applied to a set of 16 substrates, tetra- and pentasubstituted oxazepanes were prepared with good yields and moderate to excellent regio- and stereoselectivities.

  DOI：

  10.1021/jo3021715

文献信息

• Stereo- and Regioselective Synthesis of Polysubstituted Chiral 1,4-Oxazepanes
  作者：Michelle Bezanson、Joshua Pottel、Rana Bilbeisi、Sylvestre Toumieux、Mickaël Cueto、Nicolas Moitessier

  DOI：10.1021/jo3021715

  日期：2013.2.1

  The number of cyclic molecular scaffolds available to medicinal chemists remains limited, and simple structures such as oxazepanes are still made using multistep procedures, including a number of protection/deprotection steps and purifications. We report herein an expedient and efficient synthesis of chiral polysubstituted oxazepanes. The developed method relies on a regio- and stereoselective 7-endo cyclization through haloetherification. Mechanistic studies using a combination of computations and experiments confirmed the expected role of the asymmetry of the chiral bromonium intermediate on the haloetherification regioselectivity. Computations also suggested that the bromonium intermediate is formed with no transition state; hence, the stereoselectivity is controlled primarily by the conformation of the substrate. Applied to a set of 16 substrates, tetra- and pentasubstituted oxazepanes were prepared with good yields and moderate to excellent regio- and stereoselectivities.
• Fluoride-Mediated Desulfonylative Intramolecular Cyclization to Fused and Bridged Bicyclic Compounds: A Complex Mechanism
  作者：Michelle Bezanson、Anna Tomberg、Nicolas Moitessier

  DOI：10.1021/acs.joc.6b02999

  日期：2017.3.3

  the synthesis of polysubstituted chiral oxazepanes in three steps from commercially available starting materials. The unexpected reaction of one of these 1,4-oxazepanes in the presence of TBAF provided a 4-oxa-1-azabicyclo[4.1.0]heptane core. This unusual process significantly increased the complexity of the molecular scaffold by introducing a bicyclic core. Surprisingly, the generated bicyclic structure

  我们先前报道了由市售起始原料分三步合成多取代的手性恶唑烷。这些1，4-恶唑酮之一在TBAF存在下的意外反应提供了4-oxa-1-氮杂双环[4.1.0]庚烷核。这种不寻常的过程通过引入双环核心显着增加了分子支架的复杂性。出人意料的是，生成的具有三个立体中心的双环结构是对映异构体的混合物，未观察到其他非对映异构体。这些惊人的实验观察值得进一步研究。实验和计算研究相结合，揭示了一种复杂的非对映选择性机制。为观察到的这种重排提供了机械原理。