methyl 1-(3,4-dihydroxyphenyl)-2-oxocyclopentane-carboxylate | 1245654-29-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: methyl 1-(3,4-dihydroxyphenyl)-2-oxocyclopentane-carboxylate
• 英文别名: Methyl 1-(3,4-dihydroxyphenyl)-2-oxocyclopentane-1-carboxylate
• CAS: 1245654-29-8
• 化学式: C₁₃H₁₄O₅
• 分子量: 250.251
• InChiKey: LIHFNYWKQGXTFC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.26
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  83.83
• 氢给体数：
  2.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  在 sodium dithionite 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 methyl 1-(3,4-dihydroxyphenyl)-2-oxocyclopentane-carboxylate
  参考文献：
  名称：

  An oxidative coupling for the synthesis of arylated quaternary stereocentres and its application in the total synthesis of powelline and buphanidrine

  摘要：

  Catechol derivatives directly bonded to all-carbon quaternary stereocentres are prevalent in nature. An oxidative coupling strategy for the synthesis of this motif is described. Pivoting on the base-catalysed Michael addition of carbon-centred pro-nucleophiles to in situ generated ortho-benzoquinones, the method is broad in scope, high yielding and provides remarkably simple access to this challenging motif. The application of this methodology in the total synthesis of the crinane-type amaryllidaceae alkaloids (+/-)-powelline and (+/-)-buphanidrine is demonstrated and our efforts towards an enantioselective synthesis described. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.04.132

文献信息

• Laccase-catalysed α-arylation of cyclic β-dicarbonyl compounds
  作者：Jörg Pietruszka、Chuan Wang

  DOI：10.1039/c2gc35662g

  日期：——

  In this protocol we described an environmentally friendly synthesis of α-arylated cyclic β-dicarbonyl compounds employing various catechols as precursors through an oxidation/Michael addition sequence. The process proceeded under the catalysis of a commercially available laccase at room temperature with the use of aerial oxygen as the oxidant affording the products in moderate to excellent yields (36–96%)

  在该协议中，我们描述了一种环境友好的合成α-芳基化环状β-二羰基化合物的方法， 儿茶酚通过氧化/迈克尔加成序列作为前体。该过程在室温下使用市售漆酶的催化下进行，使用空气中的氧气作为氧化剂，可提供中等至极佳收率的产品（36-96％）。此外，高度功能化环戊烷通过芳基化以优异的非对映选择性（dr> 99 ：1，95％ee）合成了一个全碳四元立体中心的轴承。
• Oxidative cross-coupling reaction of catechols with active methylene compounds in an aqueous medium using an AlPO₄-supported Ru catalyst
  作者：Zen Maeno、Masanobu Yamamoto、Takato Mitsudome、Tomoo Mizugaki、Koichiro Jitsukawa

  DOI：10.1039/c8cy01425f

  日期：——

  A green oxidative coupling reaction of catechols with active methylene compounds was achieved using an AlPO4-supported Ru catalyst, where O2 and H2O were used as the ideal oxidant and solvent, respectively. The catalyst is easily separable, reusable and applicable for gram-scale syntheses.

  使用AlPO 4负载的Ru催化剂可实现邻苯二酚与活性亚甲基化合物的绿色氧化偶联反应，其中O 2和H 2 O分别用作理想的氧化剂和溶剂。该催化剂易于分离，可重复使用并可用于克级合成。
• Tyrosinases in Organic Chemistry: A Versatile Tool for the α-Arylation of β-Dicarbonyl Compounds
  作者：Roxanne Krug、Dennis Schröder、Jan Gebauer、Sanel Suljić、Yuma Morimoto、Nobutaka Fujieda、Shinobu Itoh、Jörg Pietruszka

  DOI：10.1002/ejoc.201800188

  日期：2018.4.23

  A tyrosinase‐mediated arylation reaction is presented. Starting from a variety of substituted phenols, the enzyme generates activated o‐quinones, which subsequently can undergo a 1,4‐addition towards the desired arylation products, processing a quaternary center.

  提出了酪氨酸酶介导的芳基化反应。从各种取代的苯酚的开始，酶产生激活ø -quinones，其随后可以经历1,4-加成朝向期望的芳基化产物，加工季中心。
• Exceptional Substrate Diversity in Oxygenation Reactions Catalyzed by a Bis(μ‐oxo) Copper Complex
  作者：Melanie Paul、Melissa Teubner、Benjamin Grimm‐Lebsanft、Christiane Golchert、Yannick Meiners、Laura Senft、Kristina Keisers、Patricia Liebhäuser、Thomas Rösener、Florian Biebl、Sören Buchenau、Maria Naumova、Vadim Murzin、Roxanne Krug、Alexander Hoffmann、Jörg Pietruszka、Ivana Ivanović‐Burmazović、Michael Rübhausen、Sonja Herres‐Pawlis

  DOI：10.1002/chem.202000664

  日期：2020.6.18

  2‐2‐((dimethylamino)methyl)phenyl}‐1,1,3,3‐tetramethylguanidine (L1 ), and its characterization by UV/Vis, Raman, and XAS spectroscopy, as well as cryo‐UHR‐ESI mass spectrometry, is described. We highlight selective oxygenation of a plethora of phenolic substrates mediated by [O1 ](PF6)2, which results in mono‐ and bicyclic quinones and provides an attractive strategy for designing new phenazines. The

  酪氨酸酶含有活性侧过氧化二铜 (II) 中心，作为 C−H 氧化反应中的催化活性物质。异构双（μ-氧代）二铜（III）形式的酪氨酸酶活性一直存在争议。双(μ-oxo)二铜(III)物质[Cu 2 (μ-O) 2 ( L1 ) 2 ](X) 2 ([ O1 ](X) 2 , X=PF 6 − , BF 4 −的合成, OTf − , ClO 4 − )，由新型杂化胍配体 2-2-((二甲基氨基)甲基)苯基}-1,1,3,3-四甲基胍 ( L1 ) 稳定，并通过 UV/Vis 进行表征描述了拉曼光谱和 XAS 光谱以及冷冻-UHR-ESI 质谱。我们重点介绍了 [ O1 ](PF 6 ) 2介导的大量酚类底物的选择性氧化，产生单环和双环醌，并为设计新吩嗪提供了一种有吸引力的策略。通过使用 Fukui 函数预测选择性，并将其引入酪氨酸酶模型化学中。我们的仿生催化利用分子双氧进行有机转化，并实现远远超出酶范围的底物多样性。