(R)-ethyl 2-hydroxy-2-(5-methylthiophen-2-yl)acetate | 1191070-44-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (R)-ethyl 2-hydroxy-2-(5-methylthiophen-2-yl)acetate
• 英文别名: (S)-(5-methyl-thiophen-2-yl)hydroxyacetic acid ethyl ester；ethyl (2S)-2-hydroxy-2-(5-methylthiophen-2-yl)acetate
• CAS: 1191070-44-6
• 化学式: C₉H₁₂O₃S
• 分子量: 200.258
• InChiKey: IWOGVVKSIVGRGS-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  74.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  C₁₂H₂₀O₃SSi 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.0h， 生成 (R)-ethyl 2-hydroxy-2-(5-methylthiophen-2-yl)acetate
  参考文献：
  名称：

  Catalytic and highly enantioselective Friedel–Crafts type reactions of heteroaromatic compounds with trifluoropyruvate and glyoxylate by a dicationic palladium complex

  摘要：

  The highly enantioselective Friedel-Crafts alkylation of furan and thiophene derivatives with trifluoropyruvate, which have never provided the high level of asymmetric induction and yield until now, was achieved by using dicationic palladium complexes as Lewis acid catalysts. Moreover, glyoxylate instead of trifluoropyruvate as an electrophile led to complete change of regioselectivity with 2-trimethylsilylated furan, thiophene, and pyrrole derivatives to give the corresponding heteroarylated products in high yields and enantioselectivities. The respective products with trifluoropyruvate and glyoxylate could also be obtained via sequential catalytic reaction; intramolecular cyclization of alkynyldiols using cationic Au catalyst followed by Friedel-Crafts type reactions using dicationic Pd catalyst. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.06.013

文献信息

• Highly Enantioselective Friedel−Crafts Reaction of Thiophenes with Glyoxylates: Formal Synthesis of Duloxetine
  作者：Jakub Majer、Piotr Kwiatkowski、Janusz Jurczak

  DOI：10.1021/ol901906r

  日期：2009.10.15

  2-substituted thiophenes with alkyl glyoxylates has been developed using a catalytic amount of an easy accessible 6,6′-dibromo-BINOL/Ti(IV) complex. A variety of hydroxy(thiophene-2-yl)acetates can be synthesized in high enantioselectivites (92−98% ee) and good yields. This is the first report on the efficient asymmetric F−C reaction of thiophenes with alkyl glyoxylates. Starting from simple thiophene and n-butyl

  一系列2-取代的噻吩与乙醛酸烷基酯的有效Friedel-Crafts反应已使用催化量的易获得的6,6'-二溴-BINOL / Ti（IV）络合物进行了开发。可以高对映体选择性（92-98％ee）和高收率合成各种羟基（噻吩-2-基）乙酸酯。这是有关噻吩与乙醛酸烷基酯的有效不对称FC反应的第一个报道。从简单的噻吩和乙醛酸正丁酯开始，我们证明了度洛西汀的形式合成。
• Enantioselective Friedel-Crafts Alkylation of Thiophenes with Ethyl Glyoxylate: Easy Access to Chiral Secondary Alcohols
  作者：Zhong Huang、Jingchang Zhang、Yuqiang Zhou、Nai-Xing Wang

  DOI：10.1002/ejoc.201001455

  日期：2011.2

  Friedel–Crafts alkylation reactions of ethyl glyoxylate with various thiophenes to give the corresponding chiral secondary alcohols were demonstrated. The majority of these reactions proceeded with good enantioselectivities (up to 91 %) and satisfactory isolated yields. Notably, we found that 2-substituted thiophenes underwent the reaction more smoothly than unsubstituted and 3-substituted thiophenes

  乙醛酸乙酯与各种噻吩的 Friedel-Crafts 烷基化反应得到了相应的手性仲醇。大多数这些反应以良好的对映选择性（高达 91%）和令人满意的分离产率进行。值得注意的是，我们发现 2-取代的噻吩比未取代和 3-取代的噻吩反应更顺利。