(Z)-1-(methoxycarbonylmethylene)-1,3-dihydroisobenzofuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异香豆素
• 英文名称: (Z)-1-(methoxycarbonylmethylene)-1,3-dihydroisobenzofuran
• 英文别名: (Z)-methyl 2-[isobenzofuran-1-(3H)-ylidene]acetate；methyl (2Z)-2-(3H-2-benzofuran-1-ylidene)acetate
• 化学式: C₁₁H₁₀O₃
• 分子量: 190.199
• InChiKey: ZBKIPYAIEYEJAI-POHAHGRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl 3-[(2-iodobenzyl)oxy]acrylate 在 四丁基氯化铵 、 palladium diacetate 、 potassium carbonate 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 8.0h， 以62%的产率得到(Z)-1-(methoxycarbonylmethylene)-1,3-dihydroisobenzofuran
  参考文献：
  名称：

  Phosphine/Palladium-Catalyzed Syntheses of Alkylidene Phthalans, 3-Deoxyisoochracinic Acid, Isoochracinic Acid, and Isoochracinol

  摘要：

  In this study we used sequential catalysis-PPh3-catalyzed nucleophilic addition followed by Pd(0)-catalyzed Heck cyclization-to construct complex functionalized alkylidene phthalans rapidly, in high yields, and with good stereoselectivities (E/Z ratios of up to 1:22). The scope of this Michael-Heck reaction includes substrates bearing various substituents around the alkylidene phthalan backbone. Applying this efficient sequential catalysis, we accomplished concise total syntheses of 3-deoxyisoochacinic acid, isoochracinic acid, and isoochracinol.

  DOI：

  10.1021/ol301154f

文献信息

• Synthesis of 1-(Alkoxycarbonyl)methylene-1,3-dihydroisobenzofurans and 4-(Alkoxycarbonyl)benzo[c]pyrans by Palladium-Catalysed Oxidative Carbonylation of 2-Alkynylbenzyl Alcohols, 2-Alkynylbenzaldehydes and 2-Alkynylphenyl Ketones
  作者：Alessia Bacchi、Mirco Costa、Nicola Della Cà、Marcella Fabbricatore、Alessia Fazio、Bartolo Gabriele、Cristina Nasi、Giuseppe Salerno

  DOI：10.1002/ejoc.200300577

  日期：2004.2

  A direct synthesis of 1-(alkoxycarbonyl)methylene-1,3-dihydroisobenzofurans 2 and 5 and 4-(alkoxycarbonyl)benzo[c]pyrans 3 and 6 by oxidative Pd-catalysed cyclization/alkoxycarbonylation of 2-alkynylbenzyl alcohols 1, and of 2-alkynylbenzaldehydes or 2-alkynylphenyl ketones 4 is reported. Reactions were carried out in ROH or CH3CN/ROH (R = Me, iPr) as the solvent at 70−105 °C in the presence of catalytic

  通过氧化钯催化环化/烷氧基羰基化 2-炔基苄醇 1 和 4-(烷氧基羰基)苯并 [c] 吡喃 3 和 6 的直接合成 1-(烷氧基羰基) 亚甲基-1,3-二氢异苯并呋喃 2 和 5报道了 2-炔基苯甲醛或 2-炔基苯基酮 4。反应在作为溶剂的 ROH 或 CH3CN/ROH（R ​​= Me，iPr）中进行，温度为 70-105 °C，在催化量的 PdI2 与 KI 的存在下，在 4:1 或 3:1 的 CO/空气中混合物（25 °C 时的总压力为 2.0 或 3.2 MPa）。该反应通过亲核氧原子（已经存在于起始材料中，如 1 中，或通过 ROH 对羰基的攻击原位产生，如 4 中）在与 PdII 配位的三键上发生分子内攻击，然后进行烷氧基羰基化. 在炔烃末端位置和羟基的α碳原子上存在取代基对形成五元环或六元环的过程的选择性起着关键作用。(© Wiley-VCH Verlag GmbH &
• Phosphine/Palladium-Catalyzed Syntheses of Alkylidene Phthalans, 3-Deoxyisoochracinic Acid, Isoochracinic Acid, and Isoochracinol
  作者：Yi Chiao Fan、Ohyun Kwon

  DOI：10.1021/ol301154f

  日期：2012.7.6

  In this study we used sequential catalysis-PPh3-catalyzed nucleophilic addition followed by Pd(0)-catalyzed Heck cyclization-to construct complex functionalized alkylidene phthalans rapidly, in high yields, and with good stereoselectivities (E/Z ratios of up to 1:22). The scope of this Michael-Heck reaction includes substrates bearing various substituents around the alkylidene phthalan backbone. Applying this efficient sequential catalysis, we accomplished concise total syntheses of 3-deoxyisoochacinic acid, isoochracinic acid, and isoochracinol.