(Z)-3-(2-methoxyethylidene)isobenzofuran-1(3H)-one

• 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)-3-(2-methoxyethylidene)isobenzofuran-1(3H)-one
• 英文别名: 3-(Z-Methoxyvinylidene)phthalide；(3Z)-3-(2-methoxyethylidene)-2-benzofuran-1-one
• 化学式: C₁₁H₁₀O₃
• 分子量: 190.199
• InChiKey: XBCRKAFHEPVVBH-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

• 作为反应物：
  描述：

  (Z)-3-(2-methoxyethylidene)isobenzofuran-1(3H)-one 在 C₃₈H₄₈IrNOP⁽¹⁺⁾*C₃₂H₁₂BF₂₄^(1-) 、 氢气 作用下， 以 二氯甲烷 为溶剂， 25.0 ℃ 、1.01 MPa 条件下， 反应 24.0h， 以89%的产率得到
  参考文献：
  名称：

  Ir-SpinPHOX催化3-亚萘二甲酸酯的对映选择性加氢

  摘要：

  使用基于螺[4,4] -1,6-壬二烯的膦-恶唑啉配体（SpinPHOX）的Ir I络合物作为催化剂开发了3种亚萘二甲酸酯的第一个不对称氢化反应，提供了多种手性3出色的对映体过量（最高ee达98％）的预取代邻苯二甲酸酯。该协议的实用性已在手性药物NBP和BZP前体以及天然产物创心酚和邻苯二甲酰亚胺的不对称合成中得到证明。

  DOI：

  10.1002/anie.201807639
• 作为产物：
  描述：

  2-碘苯甲酸 、 甲基炔丙基醚 在 copper(l) iodide 、 caesium carbonate 作用下， 以 二甲基亚砜 为溶剂， 反应 12.0h， 生成 (Z)-3-(2-methoxyethylidene)isobenzofuran-1(3H)-one 、 3-(methoxymethyl)-1H-isochromen-1-one
  参考文献：
  名称：

  通过温度控制从2-碘苯甲酸和炔烃区域选择性一锅法合成异香豆素和邻苯二甲酸酯

  摘要：

  AbstractCopper‐catalyzed coupling reaction of 2‐iodobenzoic acids and alkynes such as terminal acetylenes, alkynyl carboxylic acids, and trimethylsilylacetylene selectively afforded isocoumarins and phthalides in the presence of cesium carbonate (Cs2CO3) and dimethyl sulfoxide (DMSO). Among the regioselective products, only the 6‐endo‐dig product, isocoumarin, was formed at 100 °C, and the 5‐exo‐dig product, phthalide, was formed as a major product at 25 °C. A variety of alkynes produced the corresponding isocoumarins and phthalides in good yields. A mechanism is suggested in which the formation of 2‐alkynylbenzoic acid as an intermediate via Sonogashira‐type coupling was ruled out in the reaction pathway.magnified image

  DOI：

  10.1002/adsc.201300561

文献信息

• Copper-Catalyzed Preparation of γ-Alkylidenebutenolides and Isocoumarins under Mild Palladium-Free Conditions
  作者：Samuel Inack-Ngi、Raphaël Rahmani、Laurent Commeiras、Gaëlle Chouraqui、Jérôme Thibonnet、Alain Duchêne、Mohamed Abarbri、Jean-Luc Parrain

  DOI：10.1002/adsc.200800757

  日期：2009.3

  Abstractmagnified imageA general and efficient copper(I)‐catalyzed cross‐coupling and heterocyclization reaction of terminal alkynes and β‐iodo‐α,β‐unsaturated acid derivatives has been developed under very mild conditions. This method provides easy access from good to excellent yields of a variety of 5‐ylidenebutenolides and 3‐substituted isocoumarins with excellent regio‐ and stereoselectivity. This procedure does not require the use of any expensive supplementary additives, and is palladium‐free.
• Synthesis of Isocoumarins from o-Iodobenzoic Acid and Terminal Acetylenes Mediated by Palladium Complexes and Zinc Chloride
  作者：Hong-Yueh Liao、Chien-Hong Cheng

  DOI：10.1021/jo00117a023

  日期：1995.6

  o-Iodobenzoic acid (1) reacts with various terminal acetylenes (HC=CR) in the presence of Pd(PPh(3))(4), Et(3)N, and ZnCl2 in DMF to give the corresponding 3-substituted isocoumarins (C6H4COOC(R)CH: R = n-C4H9 (2a); n-C3H7 (3a); CH2OCH3 (4a); C(CH3)(2)OH (5a); CH2OH (6a); C6H5 (7a);p-CH3C6H4 (8a); 1-cyclohexenyl (9a); o-NH2C6H4 (10a)) in fair to excellent yields, In some of these catalytic reactions, substituted isocoumarin b (C6H4COOC(R)C(C=CR)) and alkylidenephthalide c were isolated in a few percent yields, Under similar conditions, treatment of 1 with a trimethylsilyl 1,3-diyne 12 led to the formation of products 3-(2-indolyl)isocoumarin (13) and an indolylphthalide 14 in a 95:5 ratio. The reaction of o-1-pentynylbenzoic acid with ZnCl2 and Et(3)N gave 3a as the sole product indicating that ZnCl2 is likely responsible for the selective formation of the six-membered isocoumarin ring, Based on this observation and the known palladium chemistry, a mechanism involving the participation of palladium complexes in the alkynylation of 1 and zinc chloride in the heteroannulation of the reaction intermediate o-1-alkynylbenzoate is proposed for the present catalytic reactions.