6,8-dibromo-3-nitro-2H-chromene | 92210-57-6

• 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: 6,8-dibromo-3-nitro-2H-chromene
• CAS: 92210-57-6
• 化学式: C₉H₅Br₂NO₃
• 分子量: 334.952
• InChiKey: ARCGMNNISUIZCQ-UHFFFAOYSA-N

物化性质

• 熔点：
  142.6-143.8 °C(Solv: hexane (110-54-3))
• 沸点：
  413.1±45.0 °C(Predicted)
• 密度：
  2.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-1-phenyl-3-(2-(tosylamino)phenyl)prop-2-en-1-one 、 6,8-dibromo-3-nitro-2H-chromene 在 3-((3,5-bis(trifluoromethyl)phenyl)amino)-4-(((S)-(6-methoxyquinoline-4-yl))((1S,2S,4S,5R-5-vinylquinuclidine-2-yl)methyl)amino)cyclobutan-3-ene-1,2-dione 作用下， 以 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 0.17h， 以97%的产率得到2-[(6aS,7R,12aR)-2,4-dibromo-6a-nitro-12-tosyl-6a,7,12,12a-tetrahydrochromano[4,3-b]quinolin-7-yl]-1-phenylethanone
  参考文献：
  名称：

  有机催化对映选择性级联Aza-Michael / Michael加成反应，用于合成高度官能化的四氢喹啉和四氢色氮喹啉

  摘要：

  AbstractAn efficient organocatalytic highly asymmetric cascade aza‐Michael/Michael addition reaction for the synthesis of tetrahydroquinolines and tetrahydrochromanoquinolines has been developed. This cascade reaction proceeds well at low catalyst loading with a broad substrate scope, furnishing the desired products in excellent yields with excellent diastereoselectivities and enantioselectivities (up to >99:1 dr, 99% ee) under mild conditions. Importantly, it is the first catalytic asymmetric method for tetrahydrochromanoquinolines. This protocol provides a straightforward entry to highly functionalized chiral tetrahydroquinoline and tetrahydrochromanoquinoline derivatives from simple starting materials.magnified image

  DOI：

  10.1002/adsc.201300670
• 作为产物：
  描述：

  3,5-二溴水杨醛 、 2-硝基乙醇 在 二正丁胺盐酸盐 作用下， 以 various solvent(s) 为溶剂， 反应 6.5h， 以46%的产率得到6,8-dibromo-3-nitro-2H-chromene
  参考文献：
  名称：

  A Convenient One-Pot Synthesis of 2-Unsubstituted 3-Nitro-2H-chromenes

  摘要：

  DOI：

  10.1055/s-1984-30841

文献信息

• Organocatalytic Oxa-Michael/Michael/Michael/Aldol Condensation Quadruple Domino Sequence: Asymmetric Synthesis of Tricyclic Chromanes
  作者：Mukesh Kumar、Pankaj Chauhan、Stephen J. Bailey、Ehsan Jafari、Carolina von Essen、Kari Rissanen、Dieter Enders

  DOI：10.1021/acs.orglett.8b00175

  日期：2018.2.16

  An efficient and highly stereoselective one-pot, four-component synthesis of functionalized tricyclic chromanes has been achieved through an organocatalyzed quadruple domino reaction. The reaction sequence involves an oxa-Michael/Michael/Michael/aldol condensation between alcohols, 2 equiv of acrolein, and nitrochromenes to generate the pharmaceutically important tricyclic chromanes bearing three contiguous

  通过有机催化的四重多米诺反应，已实现了高效且高度立体选择性的一锅四组分官能化三环苯并吡喃的合成。反应顺序包括在醇，2当量的丙烯醛和硝基色酮之间进行oxa-Michael / Michael / Michael / aldol缩合反应，以产生药学上重要的三环苯并三环苯并烷，其中包括三个连续的立体异构中心，包括手性四取代碳中心，具有良好的多米诺产量（30– 70％）和出色的非对映选择性和对映选择性（> 20：1 dr和> 99％ee）。
• Enantioselective Cascade Michael Addition/Cyclization Reactions of 3-Nitro-2<i>H</i>-Chromenes with 3-Isothiocyanato Oxindoles: Efficient Synthesis of Functionalized Polycyclic Spirooxindoles
  作者：Fen Tan、Liang-Qiu Lu、Qing-Qing Yang、Wei Guo、Qiao Bian、Jia-Rong Chen、Wen-Jing Xiao

  DOI：10.1002/chem.201303583

  日期：2014.3.17

  An unprecedented Zn(OTf)2‐catalyzed asymmetric Michael addition/cyclization cascade of 3‐nitro‐2H‐chromenes with 3‐isothiocyanato oxindoles has been disclosed. This transformation provides an efficient access to various synthetically important polycyclic spirooxindoles in a highly stereoselective manner under mild conditions (72–99 % yields, up to >95:5 d.r. and >99 % ee). The reaction leads to the

  公开了前所未有的Zn（OTf）2催化的3-硝基-2 H-色酮与3-异硫氰酸根合吲哚的不对称Michael加成/环化级联反应。这种转化可在温和条件下（72–99％的收率，高达> 95：5 dr和> 99％ee的情况下）以高度立体选择性的方式，有效地获得各种合成上重要的多环螺氧并吲哚类化合物 。该反应可在一次操作中形成三个连续的立体中心，包括1,3-不相邻的四取代碳立体中心。基于对照实验，提出了手性Zn（OTf）2 /双（恶唑啉）配合物的双功能激活模型，其中Zn II 分子部分起路易斯酸的作用，而游离NH基团的N原子通过氢键相互作用起路易斯碱的作用。
• Enantioselective cascade double Michael addition of 3-nitro-2H-chromenes and acyclic enones: efficient synthesis of functionalized tricyclic chroman derivatives
  作者：Jun-Hua Li、Da-Ming Du

  DOI：10.1039/c5ob01211b

  日期：——

  tetrahydro-6H-benzo[c]chromenes and their derivatives has been developed. The corresponding products were obtained by the cascade double Michael addition of 3-nitro-2H-chromenes and their derivatives with α,β-unsaturated ketones catalyzed by a combination of a quinine-derived primary amine and benzoic acid. Through this methodology, the desired products could be obtained in moderate to good yields (up to

  已经开发出用于不对称构造对映体富集的四氢-6 H-苯并[ c ]色烯及其衍生物的有效方案。相应的产物通过将3-硝基-2 H-色酮及其衍生物与奎宁衍生的伯胺和苯甲酸的组合催化的α，β-不饱和酮进行级联双迈克尔加成而获得。通过这种方法，可以以中等至良好的收率（高达90％），具有优异的非对映选择性（高达> 25：1 dr）和中等至优异的对映选择性（高达95％ee）获得所需的产物。
• Enantioselective synthesis of chiral heterocycles containing both chroman and pyrazolone derivatives catalysed by a chiral squaramide
  作者：Jun-Hua Li、Da-Ming Du

  DOI：10.1039/c4ob02653e

  日期：——

  An efficient chiral squaramide-catalysed enantioselective Michael addition of pyrazolin-5-ones to 3-nitro-2H-chromenes afforded chiral heterocycles containing both chroman and pyrazolone derivatives in high to excellent yields (up to 98%) with high enantioselectivities (up to 96%) under very low catalyst loading (0.2 mol%).

  一个高效的手性方酰胺催化的选择性马克尔加成反应，将吡唑啉-5-酮加到3-硝基-2H-色醇中，得到含有色醇和吡唑酮衍生物的手性杂环化合物，收率高达98%，对映选择性高达96%，在非常低的催化剂负载下（0.2 mol%）。
• Efficient conjugate addition of carbonyl compounds to 3-nitro-2H-chromenes in the presence of bases
  作者：Zhi-peng Hu、Jun-min Zhang、Chun-liang Lou、Jin-jia Wang、Shao-zhen Nie、and Ming Yan

  DOI：10.3998/ark.5550190.0011.a03

  日期：——

  The conjugate addition of aldehydes and ketones to 3-nitro-2H-chromenes under basic conditions has been explored. A series of inorganic and organic bases were examined. Proline combined with NaOAc was found to act as an efficient catalyst for the reaction. A number of substituted 3-nitro-2H-chromenes, aldehydes, and ketones are applicable for this transformation. trans-3-Nitro-4-substituted chromanes

  已经探索了在碱性条件下醛和酮与 3-硝基-2H-色烯的共轭加成。检查了一系列无机和有机碱。脯氨酸与 NaOAc 结合被发现作为反应的有效催化剂。许多取代的 3-硝基-2H-色烯、醛和酮都适用于这种转化。trans-3-Nitro-4-取代的色满有时以良好的产率和优异的非对映选择性获得。反式-2-甲基-2-(3-硝基色满-4-基)丙醛一步转化为顺式-2,3-二氢-1,1-二甲基-1H-色满[3,4-b]吡咯.