7-methyl-3-phenyl-3,4-dihydro-2H-1,4-benzoxazin-2-one | 1192308-07-8

• 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: 7-methyl-3-phenyl-3,4-dihydro-2H-1,4-benzoxazin-2-one
• 英文别名: 7-methyl-3-phenyl-3,4-dihydro-1,4-benzoxalin-2-one；(3R)-7-methyl-3-phenyl-3,4-dihydro-1,4-benzoxazin-2-one
• CAS: 1192308-07-8
• 化学式: C₁₅H₁₃NO₂
• 分子量: 239.274
• InChiKey: VHGMYMDMUXTCAI-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  7-甲基-3-苯基-1,4-苯并恶嗪-2-酮 在 菲啶 、 diiodo(p-cymene)ruthenium(II) dimer 、 (R_a)-4-hydroxy-2,6-diphenyldinaphtho[1,3,2]dioxaphosphepine 4-oxide 、 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、3.45 MPa 条件下， 反应 48.0h， 以90%的产率得到7-methyl-3-phenyl-3,4-dihydro-2H-1,4-benzoxazin-2-one
  参考文献：
  名称：

  Dihydrophenanthridine: A New and Easily Regenerable NAD(P)H Model for Biomimetic Asymmetric Hydrogenation

  摘要：

  A new and easily regenerable NAD(P)H model 9,10-dihydrophenanthridine (DHPD) has been designed for biomimetic asymmetric hydrogenation of imines and aromatic compounds. This reaction features the use of hydrogen gas as terminal reductant for the regeneration of the DHPD under the mild condition. Therefore, the substrate scope is not limited in benzoxazinones; the biomimetic asymmetric hydrogenation of benzoxazines, quinoxafines, and quinolines also gives excellent activities and enantioselectivities. Meanwhile, an unexpected reversal of enantioselectivity was observed between the reactions promoted by the different NAD(P)H models, which is ascribed to the different hydride transfer pathway.

  DOI：

  10.1021/ja211684v

文献信息

• Exploration of chiral diastereomeric spiroketal (SPIROL)-based phosphinite ligands in asymmetric hydrogenation of heterocycles
  作者：Siyuan Sun、Pavel Nagorny

  DOI：10.1039/d0cc03088k

  日期：——

  best ligands for these transformations, the (S,R,R)-diastereomer of SPIRAPO was found to be highly effective ligand for the reduction of 20 different heterocyclic systems with loadings as low as S/C = 10 000. This dearomatizative hydrogenation provided direct access to optically active tetrahydroquinolines in high enantioselectivities (up to 94% ee) and excellent yields (up to 99%), and was used to

  已经制备了新的和容易获得的基于手性SPIROL的二亚膦酸酯配体（SPIRAPO），并将其用于铱催化的喹啉，喹喔啉和2 H -1,4-bezoxazin-2-ones的不对称氢化。虽然结构相似的（R，R，R）-SPIRAPO和（R）-SPINOL基亚膦酸酯不是这些转化的最佳配体，但（S，R，R发现SPIRAPO的）-非对映异构体是还原20个不同S / C = 10000负载的不同杂环系统的高效配体。这种脱芳香化氢化反应可直接获得高对映选择性（高达94％的光学活性四氢喹啉） ee）和极佳的收率（高达99％），并用于生成1.75 g天然生物碱（-）-（R）-鸟苷。该方案随后被扩展以实现喹喔啉和2 H -1,4-苯并恶嗪-2-酮的不对称氢化，具有良好至优异的对映选择性。
• (S)-Mandelate-Mediated Dynamic Kinetic Resolution of α-Bromo Esters for Asymmetric Syntheses of Aminoflavones, Dihydroquinoxalinones and Dihydrobenzoxazinones
  作者：Yong Sun Park、Yoon Min Lee

  DOI：10.3987/com-09-11700

  日期：——

  (S)-Mandelate-mediated dynamic kinetic resolution of α-bromo esters in nucleophilic substitution reaction has been investigated. Reactions of various aryl amine nucleophiles in the presence of TBAI and DIEA can provide the substitution products 2 and 7-19 up to 95% yield and 96:4 dr. Also, the simple procedure with spontaneous removal of the chiral auxiliary provides a practical protocol for asymmetric

  已经研究了 (S)-扁桃酸盐介导的 α-溴酯在亲核取代反应中的动态动力学拆分。在 TBAI 和 DIEA 存在下，各种芳胺亲核试剂的反应可以提供高达 95% 的产率和 96:4 dr 的取代产物 2 和 7-19。此外，自发去除手性助剂的简单程序为二氢喹喔啉酮 20-26 和二氢苯并恶嗪酮 27-30 高达 97:3 的不对称合成提供了实用的方案。
• Dihydrophenanthridine: A New and Easily Regenerable NAD(P)H Model for Biomimetic Asymmetric Hydrogenation
  作者：Qing-An Chen、Kai Gao、Ying Duan、Zhi-Shi Ye、Lei Shi、Yan Yang、Yong-Gui Zhou

  DOI：10.1021/ja211684v

  日期：2012.2.1

  A new and easily regenerable NAD(P)H model 9,10-dihydrophenanthridine (DHPD) has been designed for biomimetic asymmetric hydrogenation of imines and aromatic compounds. This reaction features the use of hydrogen gas as terminal reductant for the regeneration of the DHPD under the mild condition. Therefore, the substrate scope is not limited in benzoxazinones; the biomimetic asymmetric hydrogenation of benzoxazines, quinoxafines, and quinolines also gives excellent activities and enantioselectivities. Meanwhile, an unexpected reversal of enantioselectivity was observed between the reactions promoted by the different NAD(P)H models, which is ascribed to the different hydride transfer pathway.