dimethyl 2-phenylchroman-3,3-dicarboxylate | 1173178-80-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: dimethyl 2-phenylchroman-3,3-dicarboxylate
• 英文别名: Dimethyl 2-phenyl-2,4-dihydrochromene-3,3-dicarboxylate；dimethyl 2-phenyl-2,4-dihydrochromene-3,3-dicarboxylate
• CAS: 1173178-80-7
• 化学式: C₁₉H₁₈O₅
• 分子量: 326.349
• InChiKey: GPDIQBDXDITIRN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  dimethyl 2-(2-(benzyloxy)benzylidene)malonate 在 三氟化硼乙醚 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 3.0h， 生成 dimethyl 2-phenylchroman-3,3-dicarboxylate
  参考文献：
  名称：

  BF3 介导的 [1,5]-氢化物位移触发环化：硫醚加入游戏

  摘要：

  1,5-氢化物位移触发了 2-(2-(苄硫基)亚苄基)丙二酸酯环化为硫杂色烷，这是首次提出的。三氟化硼作为反应促进剂是这种 C-H 活化成功的关键。量子化学计算表明，所研究的反应是通过O-BF 2 -O 螯合物进行的，这已通过 NMR 分析得到证实。

  DOI：

  10.1002/ejoc.202200547

文献信息

• Expeditious Synthesis of Benzopyrans via Lewis Acid-Catalyzed C−H Functionalization: Remarkable Enhancement of Reactivity by an <i>Ortho</i> Substituent
  作者：Keiji Mori、Taro Kawasaki、Shosaku Sueoka、Takahiko Akiyama

  DOI：10.1021/ol100316k

  日期：2010.4.16

  An expeditious construction of a benzopyran skeleton via Lewis acid-catalyzed C−H functionalization was achieved. In this process, a [1,5] hydride shift and 6-endo cyclization successively occurred to give benzopyrans. The presence of substituents ortho to the alkoxy group significantly enhanced the reactivity, affording the desired compounds in excellent chemical yields with short reaction times.

  通过路易斯酸催化的CH官能团可以快速构建苯并吡喃骨架。在这个过程中，[1,5]氢化移和6-内环化接连不断，得到苯并吡喃。烷氧基邻位取代基的存在显着提高了反应性，以较短的反应时间以优异的化学产率提供了所需的化合物。
• C−H Bond Functionalization via Hydride Transfer: Synthesis of Dihydrobenzopyrans from <i>ortho</i>-Vinylaryl Akyl Ethers
  作者：Kevin M. McQuaid、Jonathan Z. Long、Dalibor Sames

  DOI：10.1021/ol900915p

  日期：2009.7.16

  The hydride transfer initiated cyclization ("HT-cyclization") of aryl alkyl ethers, which leads to direct coupling of sp(3) C-H bonds and activated alkenes, is reported. Readily available salicylaldehyde derived ethers are converted in one step to dihydrobenzopyrans, an important class of heteroarenes frequently found in biologically active compounds. This process has not been previously reported, in contrast to known HT-cyclizations of the corresponding tert-amines ("tert-amino effect" reactions).
• BF ₃ Mediated [1,5]‐Hydride Shift Triggered Cyclization: Thioethers Join the Game
  作者：Elvira R. Zaitseva、Alexander Yu. Smirnov、Vladimir I. Timashev、Vadim I. Malyshev、Ekaterina A. Zhigileva、Andrey A. Mikhaylov、Michael G. Medvedev、Nadezhda S. Baleeva、Mikhail S. Baranov

  DOI：10.1002/ejoc.202200547

  日期：2022.7.7

  1,5-Hydride shift triggered the cyclization of 2-(2-(benzylthio)benzylidene)malonates to thiachromanes, which are presented for the first time. Boron trifluoride as a reaction promotor is the key of this C−H activation success. Quantum chemical calculations have shown that the studied reaction proceeds via a O–BF2–O chelate, which was confirmed by NMR-analysis.

  1,5-氢化物位移触发了 2-(2-(苄硫基)亚苄基)丙二酸酯环化为硫杂色烷，这是首次提出的。三氟化硼作为反应促进剂是这种 C-H 活化成功的关键。量子化学计算表明，所研究的反应是通过O-BF 2 -O 螯合物进行的，这已通过 NMR 分析得到证实。