(3R)-3-羟基-7-甲基-3H-2-苯并呋喃-1-酮 | 63113-01-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 中文名称: (3R)-3-羟基-7-甲基-3H-2-苯并呋喃-1-酮
• 英文名称: 7-Methylphthalaldehydsaeure
• 英文别名: 3-Hydroxy-7-methylphthalid；3-hydroxy-7-methyl-3H-2-benzofuran-1-one
• CAS: 63113-01-9
• 化学式: C₉H₈O₃
• 分子量: 164.161
• InChiKey: LAAXOAGMCJHXLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R)-3-羟基-7-甲基-3H-2-苯并呋喃-1-酮 在 palladium on activated charcoal sodium hydroxide 、 氢气 、 溶剂黄146 、 锌 作用下， 以 1,4-二氧六环 、 乙醚 、 乙醇 、 异丙醇 为溶剂， 反应 14.5h， 生成 2-(2-Methoxycarbonyl-3-methylbenzyl)-4-methylindan
  参考文献：
  名称：

  Aromatische Spirane, 23. Mitt.: Darstellung von unsymmetrisch substituierten Dimethyl-2,2?-Spirobiindan-1,1?-dionen

  摘要：

  Both spirodiketones 7 and 8 were obtained as a mixture (56:44) by treatment of dicarbonic acid 5 with polyphosphoric acid (PPA). 5 was accessible from dimethylester 3, synthesized by retro-Claisen reaction between 1 and 2. In the same way, 30 was obtained via 27. The preparation of the pure spiro compounds 7 and 8, resp., was achieved by aldol reaction between 9 and 10 or 9 and 16, resp. Short treatment of the resulting compounds 11 and 17 with diazomethane yielded the methylbenzoates 12 and 18. Prolonged reaction (several hours) gave the pyrazole compounds 14 and 19, resp., which were also obtained (several days) from phthalides 14 and 20. The latter were formed from the benzylidene compounds 11 and 17, resp., by heating. 11 and 17 (after hydrogenation to 15a and 21a) were cyclized either with PPA or thermically to the spiro compounds 7 and 8. The main product 20 was cyclized thermically to 8 after reduction with zinc to a mixture of 21a and 8 (20:75).

  DOI：

  10.1007/bf00810885
• 作为产物：
  描述：

  对甲苯甲酸 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 水 、 palladium diacetate 作用下， 以 苯 为溶剂， 反应 37.0h， 生成 (3R)-3-羟基-7-甲基-3H-2-苯并呋喃-1-酮
  参考文献：
  名称：

  手性双环咪唑催化的酰基动力学动力学拆分合成手性邻苯二甲酰基酯

  摘要：

  利用手性双环咪唑有机催化剂并采用连续注射工艺，已开发出另一种途径，可通过对映选择性酰化作用（3-99％ee）动态动力学拆分3-羟基邻苯二酚来有效合成手性邻苯二甲酸酯基前药。计算研究表明，一般的基础催化机理不同于广泛接受的亲核催化机理。关键过渡态的结构分析表明，催化剂与底物之间的CH-π相互作用而不是先前考虑的阳离子/π-π相互作用是引起观察到的立体控制的主要因素。

  DOI：

  10.1002/anie.202012445

文献信息

• Aromatische Spirane, 21. Mitt: Darstellung von Methylphthalaldehyds�uren und ihren Ethylund Methylestern als Synthone f�r Synthesen von methylierten 2,2?-Spirobiindandionen
  作者：H. K. Neudeck

  DOI：10.1007/bf00807401

  日期：1996.2

  The isomeric methyl phthalaldehydic acids 11 were obtained from phthalides 4 by bromation (NBS) to the 3-bromo derivatives 7 and subsequent hydrolysis with water. 4 in turn were accessible from dimethyl methyl benzoates 1 by dibromination with NBS and subsequent thermical cyclization to the bromo derivatives 3 which, on catalytic dehalogenation, afforded the phthalides 4. Reaction of 11 with methanol or ethanol gave the pseudo-esters 13 and 14, resp. Short treatment of 11 with diazomethane on the other hand yielded the methyl formyl benzoates 15b to 15e. Prolonged reaction (several hours) gave the oxiranyl compounds 17; in addition, the acetonyl derivatives 18 were also found, obviously formed by a double methylene insertion into 15. All reactions proceeded with good to excellent yields.
• Meyer,A. et al., Chemische Berichte, 1977, vol. 110, p. 1403 - 1420
  作者：Meyer,A. et al.

  DOI：——

  日期：——
• US9642836B2
  申请人：——

  公开号：US9642836B2

  公开（公告）日：2017-05-09
• Chiral Bicyclic Imidazole‐Catalyzed Acylative Dynamic Kinetic Resolution for the Synthesis of Chiral Phthalidyl Esters
  作者：Muxing Zhou、Tatiana Gridneva、Zhenfeng Zhang、Ende He、Yangang Liu、Wanbin Zhang

  DOI：10.1002/anie.202012445

  日期：2021.1.18

  Utilizing a chiral bicyclic imidazole organocatalyst and adopting a continuous injection process, an alternative route has been developed for the efficient synthesis of chiral phthalidyl ester prodrugs via dynamic kinetic resolution of 3‐hydroxyphthalides through enantioselective acylation (up to 99 % ee). The computational studies suggest a general base catalytic mechanism differing from the widely

  利用手性双环咪唑有机催化剂并采用连续注射工艺，已开发出另一种途径，可通过对映选择性酰化作用（3-99％ee）动态动力学拆分3-羟基邻苯二酚来有效合成手性邻苯二甲酸酯基前药。计算研究表明，一般的基础催化机理不同于广泛接受的亲核催化机理。关键过渡态的结构分析表明，催化剂与底物之间的CH-π相互作用而不是先前考虑的阳离子/π-π相互作用是引起观察到的立体控制的主要因素。
• Aromatische Spirane, 23. Mitt.: Darstellung von unsymmetrisch substituierten Dimethyl-2,2?-Spirobiindan-1,1?-dionen
  作者：H. K. Neudeck

  DOI：10.1007/bf00810885

  日期：1996.4

  Both spirodiketones 7 and 8 were obtained as a mixture (56:44) by treatment of dicarbonic acid 5 with polyphosphoric acid (PPA). 5 was accessible from dimethylester 3, synthesized by retro-Claisen reaction between 1 and 2. In the same way, 30 was obtained via 27. The preparation of the pure spiro compounds 7 and 8, resp., was achieved by aldol reaction between 9 and 10 or 9 and 16, resp. Short treatment of the resulting compounds 11 and 17 with diazomethane yielded the methylbenzoates 12 and 18. Prolonged reaction (several hours) gave the pyrazole compounds 14 and 19, resp., which were also obtained (several days) from phthalides 14 and 20. The latter were formed from the benzylidene compounds 11 and 17, resp., by heating. 11 and 17 (after hydrogenation to 15a and 21a) were cyclized either with PPA or thermically to the spiro compounds 7 and 8. The main product 20 was cyclized thermically to 8 after reduction with zinc to a mixture of 21a and 8 (20:75).

表征谱图