Benzyl 2-oxo-2-thiophen-2-ylacetate | 887641-79-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Benzyl 2-oxo-2-thiophen-2-ylacetate
• CAS: 887641-79-4
• 化学式: C₁₃H₁₀O₃S
• 分子量: 246.287
• InChiKey: WYNVQAHSJGPJLD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  71.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Benzyl 2-oxo-2-thiophen-2-ylacetate 在 (R,R)-QuinoxP 、 氢气 、 palladium diacetate 、 四氯化钛 、 三乙胺 作用下， 以 二氯甲烷 、 2,2,2-三氟乙醇 为溶剂， 20.0 ℃ 、100.0 kPa 条件下， 反应 24.0h， 生成 (S)-benzyl 2-((4-methylphenyl)sulfonamido)-2-(thiophen-2-yl)acetate
  参考文献：
  名称：

  Pd(OAc)₂-Catalyzed Asymmetric Hydrogenation of α-Iminoesters

  摘要：

  An efficient Pd(OAc)(2)-catalyzed asymmetric hydrogenation of alpha-iminoesters was realized for the first time at 1 atm hydrogen pressure and room temperature. Pd(OAc)(2), a less expensive Pd salt with low toxicity, was found to be the most suitable catalyst precursor rather than Pd(TFA)(2) which is usually the catalyst of choice for homogeneous asymmetric hydrogenation. The chiral alpha-arylglycine fragments are widely found in many chiral products and bioactive molecules.

  DOI：

  10.1021/acs.orglett.9b03452
• 作为产物：
  描述：

  2-乙酰基噻吩 在 吡啶 、 selenium(IV) oxide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲基叔丁基醚 为溶剂， 反应 6.0h， 生成 Benzyl 2-oxo-2-thiophen-2-ylacetate
  参考文献：
  名称：

  Pd(OAc)₂-Catalyzed Asymmetric Hydrogenation of α-Iminoesters

  摘要：

  An efficient Pd(OAc)(2)-catalyzed asymmetric hydrogenation of alpha-iminoesters was realized for the first time at 1 atm hydrogen pressure and room temperature. Pd(OAc)(2), a less expensive Pd salt with low toxicity, was found to be the most suitable catalyst precursor rather than Pd(TFA)(2) which is usually the catalyst of choice for homogeneous asymmetric hydrogenation. The chiral alpha-arylglycine fragments are widely found in many chiral products and bioactive molecules.

  DOI：

  10.1021/acs.orglett.9b03452

文献信息

• Solvent‐Mediated C3/C7 Regioselective Switch in Chiral Phosphoric Acid‐Catalyzed Enantioselective Friedel‐Crafts Alkylation of Indoles with α‐Ketiminoesters
  作者：Yunlong Zhao、Lu Cai、Tongkun Huang、Shanshui Meng、Albert S. C. Chan、Junling Zhao

  DOI：10.1002/adsc.201901380

  日期：2020.3.17

  The first solvent‐mediated tunable C3/C7 regio‐ and enantioselective Friedel‐Crafts alkylation of 4‐aminoindoles with α‐ketimino esters has been developed. This catalysis allows the highly regioselective formation of indole C3 and C7 alkylation products, both in high yields (up to 96%) and excellent enantioselectivities (up to 99% ee). Mechanism study revealed that the hydrogen‐bonding interactions

  已开发出第一个溶剂介导的带有α-酮亚胺基酯的4-氨基吲哚的C3 / C7区域和对映选择性Friedel-Crafts烷基化反应。这种催化作用可以高区域选择性地形成吲哚C3和C7烷基化产物，既具有高产率（高达96％）又具有出色的对映选择性（高达99％ee）。机理研究表明，溶剂与催化剂的氢键相互作用对区域选择性的转换起着至关重要的作用。此外，相应的产物是吲哚，其中含有带有四级立体中心的非天然α-氨基酸衍生物，并且可以进行许多进一步的修饰。
• Brønsted base-catalyzed three-component coupling reaction of α-ketoesters, imines, and diethyl phosphite utilizing [1,2]-phospha-Brook rearrangement
  作者：Azusa Kondoh、Masahiro Terada

  DOI：10.1039/c6ob00739b

  日期：——

  α-ketoesters, imines, and diethyl phosphite under Brønsted base catalysis was developed by utilizing the [1,2]-phospha-Brook rearrangement. The reaction involves the generation of ester enolates via the umpolung process, i.e., the chemoselective addition of diethyl phosphite to α-ketoesters followed by the [1,2]-phospha-Brook rearrangement, and the trapping of the resulting enolates by imines preferentially

  利用[1,2]-磷-布鲁克重排反应，在布朗斯台德碱催化下，开发了α-酮酸酯，亚胺和亚磷酸二乙酯的三组分偶联反应。该反应涉及通过聚对苯二酚过程产生酯烯酸酯，即，将亚磷酸二乙酯化学选择性加成到α-酮酸酯上，然后进行[1,2]-磷-布鲁克重排，以及亚胺比α-酮酸酯和质子优先捕获亚油酸酯。该操作简单的反应可以以高收率提供在α-位具有氧官能度的致密官能化的β-氨基酸衍生物。非对映选择性很大程度上取决于底物和反应温度，这归因于酯烯酸酯向亚胺的添加的可逆性。该方法进一步扩展到α-酮酸酯，β-硝基苯乙烯和亚磷酸二乙酯的反应。
• Asymmetric Vinylogous Aldol Reaction via H-Bond-Directing Dienamine Catalysis
  作者：David Bastida、Yankai Liu、Xu Tian、Eduardo Escudero-Adán、Paolo Melchiorre

  DOI：10.1021/ol303312p

  日期：2013.1.4

  The enantioselective direct vinylogous aldol reaction of 3-methyl 2-cyclohexen-1-one with α-keto esters has been developed. The key to success was the design of a bifunctional primary amine-thiourea catalyst that can combine H-bond-directing activation and dienamine catalysis. The simultaneous dual activation of the two reacting partners results in high reactivity while securing high levels of stereocontrol

  已经开发了3-甲基2-环己烯-1-酮与α-酮酯的对映选择性直接乙烯基醇醛缩合反应。成功的关键是双功能伯胺-硫脲催化剂的设计，该催化剂可以结合H键导向活化和二烯胺催化。两个反应伙伴的同时双重激活导致高反应性，同时又确保了高水平的立体控制。
• METHOD FOR PURIFYING PYRUVIC ACID COMPOUNDS
  申请人：SUMITOMO CHEMICAL COMPANY LIMITED

  公开号：EP0937703A1

  公开（公告）日：1999-08-25

  The present invention is directed to a method for purifying pyruvic acid compounds, which method comprises reacting a pyruvic acid compound of general formula (I): wherein R1 is an optionally substituted lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R2 is a lower alkyl group, with a bisulfite of general formula (II):         MHSO3     (II) wherein M is NH4 or an alkali metal, to give a bisulfite adduct of the pyruvic acid compound and then decomposing the adduct with an acid. According to the present invention, pyruvic acid compounds can be purified by simple and easy procedures without using purification techniques such as distillation or column chromatography, and the above method is advantageous as a process for the production on an industrial scale.

  本发明涉及一种纯化丙酮酸化合物的方法，该方法包括使通式(I)的丙酮酸化合物反应： 其中 R1 是任选取代的低级烷基、低级烯基、低级炔基、环烷基、芳基或杂环基，R2 是低级烷基，与通式（II）的亚硫酸氢盐反应： MHSO3 (II) 其中 M 为 NH4 或碱金属，以得到丙酮酸化合物的亚硫酸氢盐加合物，然后用酸分解该加合物。根据本发明，丙酮酸化合物可以通过简单易行的程序进行纯化，而无需使用蒸馏或柱层析等纯化技术，上述方法作为一种工业规模的生产工艺是非常有利的。
• US6348617B1
  申请人：——

  公开号：US6348617B1

  公开（公告）日：2002-02-19