3-(methoxymethyl)-1H-isochromen-1-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异香豆素及其衍生物
• 英文名称: 3-(methoxymethyl)-1H-isochromen-1-one
• 英文别名: 3-(methoxymethyl)isocoumarin；3-(Methoxymethyl)isochromen-1-one
• 化学式: C₁₁H₁₀O₃
• 分子量: 190.199
• InChiKey: IGLRDRDVQXFUAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 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：

  3-(methoxymethyl)-1H-isochromen-1-one 在 氢气 、 C₄₃H₄₅ClN₄Ru 、 sodium t-butanolate 作用下， 以 正己烷 为溶剂， 15.0 ℃ 、5.0 MPa 条件下， 反应 22.0h， 以70%的产率得到3-(methoxymethyl)isochroman-1-one
  参考文献：
  名称：

  配体合作指导的 Ru(II)-NHC-二胺预催化剂的设计：不对称加氢的应用和机理研究

  摘要：

  首次公开了从容易获得的手性 N-杂环卡宾 (NHC) 和手性二胺中模块化合成 Ru(II)-NHC-二胺配合物。明确定义的 Ru(II)-NHC-二胺配合物显示出独特的结构和配位化学，包括 1,2-二苯基乙二胺的不寻常的三齿配位效应。分离出的空气和水分稳定的 Ru(II)-NHC-二胺配合物可作为异香豆素、苯并噻吩 1,1-二氧化物和酮的不对称氢化的通用预催化剂。此外，在化学计量反应和核磁共振实验鉴定反应中间体的基础上，结合DFT计算，提出了可能的催化循环。

  DOI：

  10.1021/jacs.0c00985
• 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 24.0h， 生成 3-(methoxymethyl)-1H-isochromen-1-one
  参考文献：
  名称：

  钌-NHC-二胺催化异香豆素的对映选择性氢化

  摘要：

  公开了一种新颖实用的手性钌-NHC-二胺体系，用于异香豆素的对映选择性氢化，为将（手性）NHC配体应用于不对称催化提供了一个新概念。以优异的对映选择性（高达 99% ee）获得了多种光学活性 3-取代的 3,4-二氢异香豆素。此外，该方法还用于合成 O-甲基蜜蜡、蜜蜡和赭曲霉毒素 A。

  DOI：

  10.1021/jacs.6b13124

文献信息

• Palladium-Catalyzed Sequential Nucleophilic Addition/Oxidative Annulation of Bromoalkynes with Benzoic Acids To Construct Functionalized Isocoumarins
  作者：Guangbin Jiang、JianXiao Li、Chuanle Zhu、Wanqing Wu、Huanfeng Jiang

  DOI：10.1021/acs.orglett.7b01919

  日期：2017.9.1

  for the preparation of 3-substituted isocoumarins via palladium-catalyzed nucleophilic addition/oxidative annulation of bromoalkynes with benzoic acids has been developed. Remarkably, preliminary mechanistic studies indicated that the transformation might proceed via a stereo- and regioselective nucleophilic addition and C–H functionalization procedure.

  已经开发了通过钯催化的溴炔烃与苯甲酸的亲核加成/氧化环化反应制备3-取代的香豆素的有效而有效的方案。值得注意的是，初步的机理研究表明，转化可能通过立体和区域选择性亲核加成和CH功能化程序进行。
• Regioselective One-Pot Synthesis of Isocoumarins and Phthalides from 2-Iodobenzoic Acids and Alkynes by Temperature Control
  作者：Manian Rajesh Kumar、Francis Mariaraj Irudayanathan、Joong Ho Moon、Sunwoo Lee

  DOI：10.1002/adsc.201300561

  日期：2013.11.11

  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
• 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.
• Ruthenium–NHC–Diamine Catalyzed Enantioselective Hydrogenation of Isocoumarins
  作者：Wei Li、Mario P. Wiesenfeldt、Frank Glorius

  DOI：10.1021/jacs.6b13124

  日期：2017.2.22

  A novel and practical chiral ruthenium-NHC-diamine system is disclosed for the enantioselective hydrogenation of isocoumarins, which provides a new concept to apply (chiral) NHC ligands in asymmetric catalysis. A variety of optically active 3-substituted 3,4-dihydroisocoumarins were obtained in excellent enantioselectivities (up to 99% ee). Moreover, this methodology was utilized in the synthesis of

  公开了一种新颖实用的手性钌-NHC-二胺体系，用于异香豆素的对映选择性氢化，为将（手性）NHC配体应用于不对称催化提供了一个新概念。以优异的对映选择性（高达 99% ee）获得了多种光学活性 3-取代的 3,4-二氢异香豆素。此外，该方法还用于合成 O-甲基蜜蜡、蜜蜡和赭曲霉毒素 A。