(+)-2,3-dihydro-2-methyl-3-methylene-1,4-benzodioxin

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并二恶烷
• 英文名称: (+)-2,3-dihydro-2-methyl-3-methylene-1,4-benzodioxin
• 英文别名: 2-Methyl-3-methylidene-1,4-benzodioxine
• 化学式: C₁₀H₁₀O₂
• 分子量: 162.188
• InChiKey: HUAXASNSTMKZHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  邻苯二酚 、 3-methylethynyl methyl carbonate 在 tris(dibenzylideneacetone)dipalladium (0) 1,4-双(二苯基膦)丁烷 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以95%的产率得到(+)-2,3-dihydro-2-methyl-3-methylene-1,4-benzodioxin
  参考文献：
  名称：

  钯催化的2,3-二氢-2-亚甲基-1,4-苯并二恶英的合成。

  摘要：

  钯催化的苯1,2-二醇与各种炔丙基碳酸酯的缩合反应提供区域和立体选择性的2,3-二氢-2-亚甲基-1,4-苯并二恶英。建议该反应通过形成（sigma-烯基）钯配合物进行，然后苯氧化物离子在该配合物上进行分子间攻击以生成新的（sigma-烯丙基）钯配合物，与相应的（eta（ 3）-烯丙基）钯络合物。酚盐离子的分子内侵蚀得到相应的苯并二恶烷化合物。最后的攻击主要发生在（eta（3）-烯丙基）钯中间体的更亲电子的末端。产物的Z-或E-立体化学通过（1）H NMR和质子NOE测量以及在一个实施例上通过X射线分析确定。通常观察到的Z-立体化学与这种（eta（3）-烯丙基）钯中间体的形成是一致的。但是，在碳酸叔炔丙酯的情况下，通常观察到的E-立体化学可以解释为苯氧离子对中间（sigma-烯丙基）钯配合物的分子内攻击，与（eta（3）-烯丙基的平衡缓慢）钯配合物

  DOI：

  10.1021/jo0103625

文献信息

• Asymmetric palladium-catalyzed annulation of benzene-1,2-diol and racemic secondary propargylic carbonates bearing two different substituents
  作者：Norbert Dominczak、Céline Damez、Bouchra Rhers、Jean-Robert Labrosse、Paul Lhoste、Boguslaw Kryczka、Denis Sinou

  DOI：10.1016/j.tet.2005.01.084

  日期：2005.3

  The palladium-catalyzed cyclization of benzene-1,2-diol with various racemic secondary propargyl carbonates having no acetylenic hydrogen in the presence of (R)-Binap as the chiral ligand afforded the two regioisomers of the corresponding 2,3-dihydro-1,4-dioxin derivatives in quite good yields, and also in enantioselectivities going from 40 to 97%. The cyclization of benzene-1,2-diol with methyl (R)-1-methyl-3-phenylpro-2-yn-1-yl carbonate in the presence of dppb as the achiral ligand afforded 2-benzylidene-3-methyl-2,3-dihydro-1,4-benzodioxine as the major product with 15% ee. The use of (R)-Binap as the chiral ligand afforded the (+) cyclized compound in 45% ee, when the (-) enantiomer was obtained with 77% ee in the presence of (S)-Binap. All the results suggest that in this case the enantioselective step is the diastereoselective protonation of the palladium-carbene intermediates. (C) 2005 Elsevier Ltd. All rights reserved.
• An easy palladium-catalyzed access to 2-alkylidene-1,4-benzodioxanes
  作者：Jean-Robert Labrosse、Paul Lhoste、Denis Sinou

  DOI：10.1016/s0040-4039(99)01919-x

  日期：1999.12

  Palladium-catalyzed cyclization of benzene-1,2-diol with various propargylic carbonates led to 2-alkylidene1,4-benzodioxanes in excellent chemical yields. Diphosphines such as dppb, dpppe or dpph, and monophosphines are the best ligands. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Asymmetric Palladium-Catalyzed Annulation of Benzene-1,2-diols and Propargylic Carbonates
  作者：Jean-Robert Labrosse、Paul Lhoste、Denis Sinou

  DOI：10.1002/1099-0690(200206)2002:12<1966::aid-ejoc1966>3.0.co;2-w

  日期：2002.6

  The reaction of benzene-1,2-diol with various propargylic carbonates in the presence of a palladium catalyst and various chiral ligands afforded the corresponding 2-alkylidene-3-alkyl-2,3-dihydrobenzodioxins in quite good yields and enantioselectivities of up to 97%. The highest enantiomeric excesses were obtained using atropoisomeric diphosphanes as the chiral ligands; when Diop, BDPP and other ligands gave quite low enantioselectivities.
• A Simple and Efficient Enantioselective Synthesis of 2-Alkylidene-3-alkyl-1,4-benzodioxanes by Palladium-Catalyzed Annulation of Benzene-1,2-diol and Propargylic Carbonates
  作者：Jean-Robert Labrosse、Paul Lhoste、Denis Sinou

  DOI：10.1021/ol9913791

  日期：2000.2.1

  [GRAPHICS]Benzene-1,2 diol reacts with various propargylic carbonates in the presence of a palladium catalyst and a chiral atropoisomeric diphosphine to give 2 alkylidene 3-alkyl-1,4-benzodioxanes in good yields and 56-97% enantiomeric excess.
• Palladium-Catalyzed Synthesis of 2,3-Dihydro-2-ylidene-1,4-benzodioxins
  作者：Jean-Robert Labrosse、Paul Lhoste、Denis Sinou

  DOI：10.1021/jo0103625

  日期：2001.10.1

  4-benzodioxins. The reaction is suggested to proceed by the formation of a (sigma-allenyl)palladium complex, followed by the intermolecular attack of the phenoxide ion on this complex to generate a new (sigma-allyl)palladium complex in equilibrium with the corresponding (eta(3)-allyl)palladium complex. Intramolecular attack of the phenoxide ion afforded the corresponding benzodioxan compound. This last

  钯催化的苯1,2-二醇与各种炔丙基碳酸酯的缩合反应提供区域和立体选择性的2,3-二氢-2-亚甲基-1,4-苯并二恶英。建议该反应通过形成（sigma-烯基）钯配合物进行，然后苯氧化物离子在该配合物上进行分子间攻击以生成新的（sigma-烯丙基）钯配合物，与相应的（eta（ 3）-烯丙基）钯络合物。酚盐离子的分子内侵蚀得到相应的苯并二恶烷化合物。最后的攻击主要发生在（eta（3）-烯丙基）钯中间体的更亲电子的末端。产物的Z-或E-立体化学通过（1）H NMR和质子NOE测量以及在一个实施例上通过X射线分析确定。通常观察到的Z-立体化学与这种（eta（3）-烯丙基）钯中间体的形成是一致的。但是，在碳酸叔炔丙酯的情况下，通常观察到的E-立体化学可以解释为苯氧离子对中间（sigma-烯丙基）钯配合物的分子内攻击，与（eta（3）-烯丙基的平衡缓慢）钯配合物