3-[(2-fluorophenyl)methylene]-2,3-dihydro-4H-1-benzopyran-4-one | 1224712-84-8

• 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: 3-[(2-fluorophenyl)methylene]-2,3-dihydro-4H-1-benzopyran-4-one
• 英文别名: (E)-3-[1-(2-fluoro phenyl)-methylidene]-chroman-4-one；(E)-3-(2-fluorobenzylidene)-4-chromanone；(3E)-3-[(2-fluorophenyl)methylidene]chromen-4-one
• CAS: 1224712-84-8
• 化学式: C₁₆H₁₁FO₂
• 分子量: 254.261
• InChiKey: PWJDMLKGJLNPOA-FMIVXFBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 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：
  3

反应信息

• 作为反应物：
  描述：

  3-[(2-fluorophenyl)methylene]-2,3-dihydro-4H-1-benzopyran-4-one 反应 40.0h， 以54%的产率得到(2'R,3S,3'S,4'R)-3',4'-bis(2-fluorophenyl)dispiro[chromane-3,1'-cyclobutane-2',3''-chromane]-4,4''-dione
  参考文献：
  名称：

  Topochemical photodimerization of (E)-3-benzylidene-4-chromanone derivatives from β-type structures directed by halogen groups

  摘要：

  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.

  DOI：

  10.1016/j.tet.2011.09.087
• 作为产物：
  描述：

  2-((3-(2-fluorophenyl)prop-2-yn-1-yl)oxy)benzaldehyde 在 C₉H₁₄NO₂S₂⁽¹⁺⁾*ClO₄^(1-) 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以80%的产率得到3-[(2-fluorophenyl)methylene]-2,3-dihydro-4H-1-benzopyran-4-one
  参考文献：
  名称：

  N-杂环卡宾催化的级联反应涉及未活化炔烃的氢酰化

  摘要：

  报道了 N-杂环卡宾 (NHC) 催化的未活化炔烃的加氢酰化，以提供 α、β-不饱和酮。此外，涉及炔烃加氢酰化和随后的分子间 Stetter 反应的高效和选择性双重 NHC 催化级联反应的罕见情况允许形成含有 1,4-二酮部分的色满酮。

  DOI：

  10.1021/ja102130s

文献信息

• A Convenient Palladium‐Catalyzed Carbonylative Synthesis of (<i>E</i>)‐3‐Benzylidenechroman‐4‐ones
  作者：Wei‐Feng Wang、Jin‐Bao Peng、Xinxin Qi、Jun Ying、Xiao‐Feng Wu

  DOI：10.1002/chem.201900015

  日期：2019.3.7

  A convenient palladium‐catalyzed carbonylation reaction for the efficient synthesis of (E)‐3‐benzylidenechroman‐4‐ones has been developed. Using TFBen as a solid CO source, a range of substituted (E)‐3‐benzylidenechroman‐4‐ones were prepared in moderate to good yields with 2‐iodophenols and allyl chlorides as the substrates. Additionally, substituted quinolin‐4(1H)‐ones can also be obtained with 2‐iodoaniline

  已经开发了一种便捷的钯催化羰基化反应，可有效合成（E）-3-亚苄基苯并二氢吡喃-4-酮。使用TFBen作为固体CO源，以2-碘苯酚和烯丙基氯为底物，以中等至良好的收率制备了一系列取代的（E）-3-苄叉基苯并四氢吡喃-4-酮。另外，也可以以2-碘苯胺为起始原料获得取代的喹啉-4（1 H）-1 。
• Facile synthesis of spiro chromanone-tetrahydrothiophenes with three contiguous stereocenters via sulfa-Michael/aldol cascade reactions
  作者：Ya-Jian Hu、Xiao-Bing Wang、Su-Yi Li、Sai-Sai Xie、Kelvin D.G. Wang、Ling-Yi Kong

  DOI：10.1016/j.tetlet.2014.11.026

  日期：2015.1

  A novel sulfa-Michael/aldol cascade reaction of (E)-3-arylidenechroman-4-ones with 1,4-dithiane-2,5-diol has been developed. This method provides a new practical and facile approach to 4′-hydroxy-2′-aryl-4′,5′-dihydro-2′H-spiro[chroman-3,3′-thiophen]-4-ones with three contiguous stereocenters in high yields. The transformation is atom-economic with good to excellent diastereoselectivities.

  （E）-3-芳基苯并二氢吡喃-4-酮与1，4-二噻吩-2，5-二醇的新型磺胺-迈克尔/羟醛级联反应已得到开发。此方法提供了一种新的实用的和容易的方法来4'-羟基-2'-芳基-4'，5'-二氢-2' ħ -螺[色满-3,3'-噻吩] -4-酮用三个连续高产量的立体中心。该转化是原子经济的，具有良好的至优异的非对映选择性。
• 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。
• N-Heterocyclic Carbene-Catalyzed Cascade Reaction Involving the Hydroacylation of Unactivated Alkynes
  作者：Akkattu T. Biju、Nathalie E. Wurz、Frank Glorius

  DOI：10.1021/ja102130s

  日期：2010.5.5

  The N-heterocyclic carbene (NHC)-catalyzed hydroacylation of unactivated alkynes to provide alpha,beta-unsaturated ketones is reported. In addition, a rare case of an efficient and selective dually NHC-catalyzed cascade reaction involving the hydroacylation of alkynes and a subsequent intermolecular Stetter reaction allows the formation of chromanones containing a 1,4-diketone moiety.

  报道了 N-杂环卡宾 (NHC) 催化的未活化炔烃的加氢酰化，以提供 α、β-不饱和酮。此外，涉及炔烃加氢酰化和随后的分子间 Stetter 反应的高效和选择性双重 NHC 催化级联反应的罕见情况允许形成含有 1,4-二酮部分的色满酮。
• 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.