(E)-3-(3-bromobenzylidene)chroman-4-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 高异黄酮
• 英文名称: (E)-3-(3-bromobenzylidene)chroman-4-one
• 英文别名: (E)-3-(3-bromobenzylidene)-4-chromanone；2-(3-Bromophenylmethylene)-1-benzopyran-4-one；(3E)-3-[(3-bromophenyl)methylidene]chromen-4-one
• 化学式: C₁₆H₁₁BrO₂
• 分子量: 315.166
• InChiKey: KPKOOEBNUIRGTE-XYOKQWHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  (E)-3-(3-bromobenzylidene)chroman-4-one 在 三乙烯二胺 、 2,6-二甲基吡啶 、 甲酸 、 di-(1-adamantyl)-n-butylphosphine 、 N-[(1R,2R)-1,2-二苯基-2-(2-(4-甲基苄氧基)乙氨基)-乙基]-4-甲基苯磺酰胺(氯)钌(II) 、 palladium diacetate 、 potassium carbonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 32.25h， 生成 tert-butyl(((3R,4R)-3-((4'-methoxy-[1,1'-biphenyl]-3-yl)methyl)chroman-4-yl)oxy)dimethylsilane
  参考文献：
  名称：

  铑催化的3-苄叉基苯甲酮的不对称转移加氢/动力学动力学拆分

  摘要：

  通过Rh催化的不对称转移氢化反应，可以直接从（E）-3-亚苄基-苯并二氢吡喃酮中获得对映异构体富集的顺式-3-苄基-苯并二氢苯并二氢苯并二氢吡喃酚。这种转变可以降低C═C和C═O键，并以高收率形成两个立构中心，且非对映和对映选择性极好（高达> 99：1 dr，高达> 99％ee）。通过动态动力学拆分过程的一个步骤，即使用低催化剂负载量和HCO 2 H / DABCO作为氢源。

  DOI：

  10.1021/acs.orglett.1c00047
• 作为产物：
  描述：

  2,3-二氢苯并吡喃-4-酮 、 间溴苯甲醛 在 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 10.0h， 以54%的产率得到(E)-3-(3-bromobenzylidene)chroman-4-one
  参考文献：
  名称：

  铑催化的3-苄叉基苯甲酮的不对称转移加氢/动力学动力学拆分

  摘要：

  通过Rh催化的不对称转移氢化反应，可以直接从（E）-3-亚苄基-苯并二氢吡喃酮中获得对映异构体富集的顺式-3-苄基-苯并二氢苯并二氢苯并二氢吡喃酚。这种转变可以降低C═C和C═O键，并以高收率形成两个立构中心，且非对映和对映选择性极好（高达> 99：1 dr，高达> 99％ee）。通过动态动力学拆分过程的一个步骤，即使用低催化剂负载量和HCO 2 H / DABCO作为氢源。

  DOI：

  10.1021/acs.orglett.1c00047

文献信息

• Asymmetric Three-Component Cyclizations toward Structurally Spiro Pyrrolidines via Bifunctional Phosphonium Salt Catalysis
  作者：Lixiang Zhu、Xiaoyu Ren、Zhongxiu Liao、Jianke Pan、Chunhui Jiang、Tianli Wang

  DOI：10.1021/acs.orglett.9b03282

  日期：2019.11.1

  Asymmetric multicomponent reactions toward optically pure compounds are highly attractive but extremely challenging. Presented herein is a highly diastereo- and enantioselective three-component cyclization of exocyclic alkenes with aldehydes and amino esters, which was enabled by bifunctional phosphonium salt catalysts. A wide range of multiply substituted spiro pyrrolidine derivatives were prepared

  对光学纯化合物的不对称多组分反应极具吸引力，但极具挑战性。本文提出了环外烯烃与醛和氨基酯的高度非对映和对映选择性的三组分环化，其通过双官能functional盐催化剂实现。以高收率和优异的立体选择性制备了多种多取代的螺吡咯烷衍生物。值得注意的是，这是具有相转移催化体系的催化不对称三组分反应的第一个例子。
• Highly efficient construction of chiral dispirocyclic oxindole/thiobutyrolactam/chromanone complexes through Michael/cyclization cascade reactions with a rosin-based squaramide catalyst
  作者：Ning Lin、Xian-wen Long、Qing Chen、Wen-run Zhu、Bi-chuan Wang、Kai-bin Chen、Cai-wu Jiang、Jiang Weng、Gui Lu

  DOI：10.1016/j.tet.2018.05.052

  日期：2018.7

  An efficient asymmetric Michael/cyclization cascade reaction of 4-chromanones with isothiocyanato oxindoles has been revealed. Under bifunctional organocatalysis by rosin-based squaramide catalyst, a series of spiro[oxindole/thiobutyrolactam/chromanone] complexes were conveniently constructed in a highly stereoselective manner (up to 99% yields, > 20:1 dr and >99% ee). The reaction leads to the formation

  已经揭示了4-色酮与异硫氰酸根合吲哚的有效的不对称迈克尔/环化级联反应。在基于松香的方酰胺催化剂的双功能有机催化下，可以方便地以高度立体选择性的方式构建一系列螺并[oxindole / thiobutyrolactam / chromanone]配合物（高达99％的收率，> 20：1 dr和> 99％ee）。反应导致形成三个连续的立体中心和两个螺四元立体中心。
• Iodine-promoted sequential Michael and oxidative dehydrogenation processes: synthesis of trisubstituted methanes containing a coumarin and a chromone ring
  作者：Ya-Jian Hu、Neng Jiang、Sai-Sai Xie、Su-Yi Li、Jin-Shuai Lan、Ling-Yi Kong、Xiao-Bing Wang

  DOI：10.1016/j.tet.2015.08.056

  日期：2015.10

  An iodine-promoted convenient and environmentally friendly sequential method for the synthesis of trisubstituted methanes bearing a coumarin and a chromone ring is described. The remarkable features of this approach include avoidance of metals, working under air, employment of readily available starting materials, good functional group tolerance and simple operation. (C) 2015 Elsevier Ltd. All rights reserved.
• Design, synthesis and antiproliferative activity of some 3-benzylidene-2,3-dihydro-1-benzopyran-4-ones which display selective toxicity for malignant cells
  作者：Pal Perjési、Umashankar Das、Erik De Clercq、Jan Balzarini、Masame Kawase、Hiroshi Sakagami、James P. Stables、Tamas Lorand、Zsuzsanna Rozmer、Jonathan R. Dimmock

  DOI：10.1016/j.ejmech.2007.06.017

  日期：2008.4

  A series of 3-benzylidene-4-chromanones 1a-1 were prepared and their cytotoxicity towards human Molt 4/C8 and CEM T-lymphocytes as well as murine L1210 lymphoid leukemia cells were compared to the previously generated biodata in these three assays for the isosteric 2-benzylidene- 1-tetralones 2a-1. Over 40% of the compounds in series 1 were more potent than their counterparts in series 2, while equipotency was noted in one-third of the comparisons made. In general the IC(50) values of 1a-1 towards the human T-lymphocytes were in the low micromolar range. Molecular modelling revealed differences in shapes of representative molecules in series 1 and 2 which may contribute to the variation in cytotoxic potencies. Most of the compounds in series 1 displayed greater potencies towards HSC-2, HSC-3, HSC-4 and HL-60 neoplasms than HGF, HPC, and HPLF normal cells and were well tolerated in mice. (c) 2007 Elsevier Masson SAS. All rights reserved.
• Topochemical photodimerization of (E)-3-benzylidene-4-chromanone derivatives from β-type structures directed by halogen groups
  作者：Xue-Ming Cheng、Zhi-Tang Huang、Qi-Yu Zheng

  DOI：10.1016/j.tet.2011.09.087

  日期：2011.11

  Halogen substituent plays an important role in the crystalline packing of aromatic compounds. The [2+2] photocycloaddition of (E)-3-benzylidene-4-chromanones in the crystalline state was investigated, and halogen substitution has been adopted to organize molecules with proper arrangement for photodimerization. Not halogen bonds, but the electron-withdrawing property of halogen atoms can enhance the face-to-face pi-pi interactions. Therefore, F, Cl or Br substitution at the para position of phenyl gave rise to almost the same beta-structures with face-to-face pi-stacking. Only resulted beta-structures can undergo photodimerization, which gave the syn-HH (syn-head-to-head) products with high regio-/stereoselectivity. (C) 2011 Elsevier Ltd. All rights reserved.