(3S,4R)-4-bromo-3-phenyl-3,4-dihydro-1H-2-benzopyran-1-one | 1354004-75-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (3S,4R)-4-bromo-3-phenyl-3,4-dihydro-1H-2-benzopyran-1-one
• 英文别名: 4-bromo-3,4-dihydro-3-phenylisochromen-1-one；(3S,4R)-4-bromo-3,4-dihydro-3-phenylisochromen-1-one；trans-4-Bromo-3-phenyl-3,4-dihydroisocoumarin；(3S,4R)-4-bromo-3-phenyl-3,4-dihydroisochromen-1-one
• CAS: 1354004-75-3
• 化学式: C₁₅H₁₁BrO₂
• 分子量: 303.155
• InChiKey: OSKMAPNZVBVQBU-KGLIPLIRSA-N

物化性质

• 沸点：
  419.8±45.0 °C(Predicted)
• 密度：
  1.498±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3S,4R)-4-bromo-3-phenyl-3,4-dihydro-1H-2-benzopyran-1-one 在 lithium aluminium tetrahydride 、 水 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以45%的产率得到(2-((2S,3S)-3-phenyloxiran-2-yl)phenyl)methanol
  参考文献：
  名称：

  An Enantioselective Approach toward 3,4-Dihydroisocoumarin through the Bromocyclization of Styrene-type Carboxylic Acids

  摘要：

  A facile and enantioselective approach toward 3,4-dihydroisocoumarin was developed. The method involved an amino-thiocarbamate catalyzed enantioselective bromocyclization of styrene-type carboxylic acids, yielding 3-bromo-3,4-dihydroisocoumarins with good yields and ee's. 3-Bromo-3,4-dihydroisocoumarins are versatile building blocks for various dihydroisocoumarin derivatives in which the Br group can readily be modified to achieve biologically important 4-O-type and 4-N-type 3,4-dihydroisocoumarin systems. In addition, studies indicated that, by refining some parameters, the synthetically useful 5-exo phthalide products could be achieved with good yields and ee's.

  DOI：

  10.1021/jo202221c
• 作为产物：
  描述：

  (E)-2-styrylbenzoic acid 在 N-溴代丁二酰亚胺(NBS) 、 O-[(S)-[(2R,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methyl] N-(2,4-dimethoxyphenyl)carbamothioate 作用下， 以 二氯甲烷 为溶剂， 反应 120.0h， 生成 (3S,4R)-4-bromo-3-phenyl-3,4-dihydro-1H-2-benzopyran-1-one 、 3-[bromo(phenyl)methyl]isobenzofuran-1(3H)-one
  参考文献：
  名称：

  An Enantioselective Approach toward 3,4-Dihydroisocoumarin through the Bromocyclization of Styrene-type Carboxylic Acids

  摘要：

  A facile and enantioselective approach toward 3,4-dihydroisocoumarin was developed. The method involved an amino-thiocarbamate catalyzed enantioselective bromocyclization of styrene-type carboxylic acids, yielding 3-bromo-3,4-dihydroisocoumarins with good yields and ee's. 3-Bromo-3,4-dihydroisocoumarins are versatile building blocks for various dihydroisocoumarin derivatives in which the Br group can readily be modified to achieve biologically important 4-O-type and 4-N-type 3,4-dihydroisocoumarin systems. In addition, studies indicated that, by refining some parameters, the synthetically useful 5-exo phthalide products could be achieved with good yields and ee's.

  DOI：

  10.1021/jo202221c

文献信息

• Design of Chiral Bifunctional Dialkyl Sulfide Catalysts for Regio‐, Diastereo‐, and Enantioselective Bromolactonization
  作者：Ryuichi Nishiyori、Ayano Tsuchihashi、Ayaka Mochizuki、Kazuma Kaneko、Masahiro Yamanaka、Seiji Shirakawa

  DOI：10.1002/chem.201803703

  日期：2018.11.13

  effective chiral dialkyl sulfide organocatalysts remain relatively rare and under‐developed, despite the potential utility of dialkyl sulfide catalysts. Herein, we report the development of chiral bifunctional dialkyl sulfide catalysts possessing a urea moiety for regio‐, diastereo‐, and enantioselective bromolactonization. The importance of the bifunctional design of chiral sulfide catalysts was clearly

  尽管已经开发出多种用于不对称转化的手性有机催化剂，但是尽管有潜在的实用性，但有效的手性二烷基硫醚有机催化剂仍然相对较少且开发不足。本文中，我们报道了具有脲部分的手性双官能二烷基硫醚催化剂的开发，该脲部分用于区域，非对映和对映选择性溴内酯化。手性硫化物催化剂的双功能设计的重要性在本工作中得到了明确证明。根据实验和理论研究的结果，阐明了催化剂的硫化物和脲部分的作用。
• Catalyst-Controlled Regio- and Stereoselective Bromolactonization with Chiral Bifunctional Sulfides
  作者：Ayano Tsuchihashi、Seiji Shirakawa

  DOI：10.1055/s-0037-1610716

  日期：2019.9

  Highly regioselective 5-exo bromolactonizations of stilbene-type carboxylic acids bearing electron-withdrawing substituents are achieved for the first time via the use of chiral bifunctional sulfide catalysts possessing a urea moiety. The chiral phthalide products are obtained in moderate to good enantioselectivities as the result of 5-exo cyclizations.

  通过使用具有尿素部分的手性双功能硫化物催化剂，首次实现了具有吸电子取代基的二苯乙烯型羧酸的高度区域选择性 5-外溴内酯化。作为 5-exo 环化的结果，手性苯酞产物以中等至良好的对映选择性获得。
• Catalytic asymmetric bromolactonization reactions using (DHQD)2PHAL-benzoic acid combinations
  作者：Alan Armstrong、D. Christopher Braddock、Alexander X. Jones、Stacy Clark

  DOI：10.1016/j.tetlet.2013.10.043

  日期：2013.12

  Catalytic (DHQD)2PHAL as modified by added benzoic acid, is an off-the-shelf catalyst-additive combination for effecting catalytic asymmetric bromolactonization reactions. This combination delivers bromolactones with asymmetric induction at a comparable level to bespoke catalysts previously optimized for particular substrate classes.

  由添加的苯甲酸改性的催化（DHQD）2 PHAL是用于实现催化不对称溴化反应的现成催化剂-添加剂组合。这种组合可提供与以前为特定底物类型优化的定制催化剂相当的不对称诱导溴内酯。
• 5-<i>exo</i>-Selective asymmetric bromolactonization of stilbenecarboxylic acids catalyzed by phenol-bearing chiral thiourea
  作者：Masayuki Sugano、Tsubasa Inokuma、Yousuke Yamaoka、Ken-ichi Yamada

  DOI：10.1039/d3ob01895d

  日期：——

  We developed a novel thiourea Lewis-base catalyst with phenol moieties for the enantioselective 5-exo-bromolactonization of stilbenecarboxylic acids to afford chiral 3-substituted phthalides. The phenol moieties are crucial for the enantio- and regio-selectivity.

  我们开发了一种带有苯酚部分的新型硫脲路易斯碱催化剂，用于二苯乙烯甲酸的对映选择性 5-外型-溴内酯化反应，得到手性 3-取代的苯并呋喃酮。苯酚部分对于对映体和区域选择性至关重要。
• The use of 2-phenyltetralin derivatives, or heterocyclic analogues, in medicine and pharmaceutical compositions containing them
  申请人：THE WELLCOME FOUNDATION LIMITED

  公开号：EP0025598A1

  公开（公告）日：1981-03-25

  Known and novel compounds of formula (i) wherein E is a sulphur atom or a NH or CH2 group, J is a nitrogen atom or a CH group, Q is a sulphur atom or a NR3 or CHR3 group, Z is oxygen or sulphur atom or a NR4 or CHR4 group and R' represents four substituents and R2 represents five substituents, provided at least three of E, J, Q, and Z are methylene residues, are active against viruses, especially rhinoviruses. Methods for producing the compounds are described, as are pharmaceutical formulations and methods for administering the compounds to cure or prevent rhinoviral infections.

  已知和新型的式(i)化合物 其中 E 是硫原子或 NH 或 CH2 基团，J 是氮原子或 CH 基团，Q 是硫原子或 NR3 或 CHR3 基团，Z 是氧或硫原子或 NR4 或 CHR4 基团，R'代表四个取代基，R2 代表五个取代基，条件是 E、J、Q 和 Z 中至少有三个是亚甲基残基。本文介绍了生产这些化合物的方法，以及使用这些化合物治疗或预防鼻病毒感染的药物制剂和方法。