ethyl 2-bromo-2-methyl-3-oxo-3-phenylpropanoate | 724762-33-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2-bromo-2-methyl-3-oxo-3-phenylpropanoate
• 英文别名: 2-bromo-2-methyl-3-oxo-3-phenyl-propionic acid ethyl ester；2-Brom-2-methyl-3-oxo-3-phenyl-propionsaeure-aethylester
• CAS: 724762-33-8
• 化学式: C₁₂H₁₃BrO₃
• 分子量: 285.137
• InChiKey: TVAGRICZFOETCO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 2-bromo-2-methyl-3-oxo-3-phenylpropanoate 在 sodium tetrahydroborate 、 三苯基膦 作用下， 生成 2-amino-3-hydroxy-2-methyl-3-phenylpropanoic acid
  参考文献：
  名称：

  带有刚性连接的手性固定碱性基团的吡pyr醛衍生物催化的氨基酸反应中的立体选择性-转氨，消旋，脱羧，逆醛醇缩合反应和醛醇缩合。

  摘要：

  四氢喹啉环用于安装吡ido醛的关键官能团，以及两个刚性固定的手性安装的碱性基团的例子。他们能够选择性催化氨基酸的脱羧，醛醇反应和逆醛醇反应，而不是氨基转移，并且具有立体选择性。在甘氨酸与乙醛的醛醇缩醛反应中合成苏氨酸和异苏氨酸，当碱性基团被质子化时，其中一种催化剂逆转了其立体选择性。观察到的立体选择性均与预测一致。

  DOI：

  10.1016/s0968-0896(02)00334-6
• 作为产物：
  描述：

  丙酸乙酯 在 四氯化碳 、 溴 、 sodium ethanolate 作用下， 生成 ethyl 2-bromo-2-methyl-3-oxo-3-phenylpropanoate
  参考文献：
  名称：

  Rapidly distinguishing reversible and irreversible CYP450 inhibitors by using fluorometric kinetic analyses

  摘要：

  In this study we have evaluated the reliability of a fluorescence-based method used for rapid identification of irreversible CYP inhibitors (mechanism-based inhibitors). This was accomplished by comparing the time-dependence pattern of IC50 values from fluorometric kinetic measurements. For irreversible CYP inhibitors, IC50 values decreased as incubation proceeded. This was due to progressive inactivation of corresponding enzymes by reactive metabolites generated during the incubation. This change pattern was confirmed using a number of known irreversible CYP inhibitors, including furafylline, midazolam, erythromycin, clarithromycin, oleandomycin, 17alpha-ethynylestradiol and verapamil. The pattern was different in reversible inhibition, depending upon the compounds tested in the fluorometric kinetic assay. For some compounds, such as clotrimazole, IC50 values remained relatively stable, whereas other compounds, such as miconazole, terfenadine and ketoconazole showed a significant increase with incubation time. Monitoring tested compounds by LC-MS/MS during the incubation confirmed that increases of IC50 were probably caused by the loss of inhibitors, resulting from either metabolic degradation, or non-specific binding to microsomal proteins.

  DOI：

  10.1007/bf03192339

文献信息

• Catalytic Enantioselective Chlorination and Bromination of β-Keto Esters
  作者：Lukas Hintermann、Antonio Togni

  DOI：10.1002/1522-2675(20000906)83:9<2425::aid-hlca2425>3.0.co;2-v

  日期：2000.9.6

  3-dioxolane-4,5-dimethanolato(2−)-O,O′]titanium ((R)-1b) are efficient catalysts for the electrophilic enantioselective chlorination and bromination of β-keto esters with N-chlorosuccinimide (NCS) and N-bromosuccinimide (NBS), respectively. With 5 mol-% of catalyst at room temperature an enantioselectivity of up to 88% ee could be obtained for the chlorination reaction. Under comparable conditions, bromination

  Ti(TADDOLato) 络合物二氯[(4R,5R)-2,2-二甲基-α,α,α',α'-四苯基-1,3-二氧戊环-4,5-二甲醇合(2-)-O, O']钛((R)-1a)和二氯[(4R,5R)-2,2-二甲基-α,α,α',α'-四(萘-1-基)-1,3-二氧戊环-4,5-二甲醇(2-)-O,O']钛((R)-1b)是β-酮酯与N-氯代琥珀酰亚胺(NCS)和N-溴代琥珀酰亚胺的亲电子对映选择性氯化和溴化的有效催化剂（国家统计局），分别。在室温下使用 5 mol-% 的催化剂，氯化反应可以获得高达 88% ee 的对映选择性。在可比较的条件下，溴化反应较慢且立体选择性较低。
• Vanadium-catalyzed oxidative bromination promoted by Brønsted acid or Lewis acid
  作者：Kotaro Kikushima、Toshiyuki Moriuchi、Toshikazu Hirao

  DOI：10.1016/j.tet.2010.06.042

  日期：2010.8

  The oxidative bromination of arenes was induced by a vanadium catalyst in the presence of a bromide salt and a Brønsted acid or a Lewis acid under molecular oxygen, which provides an eco-friendly bromination method as compared with a conventional bromination one with bromine. This catalytic reaction could be applied to the bromination of alkenes and alkynes to give the corresponding vic-bromides. Use

  芳烃的氧化溴化反应是在分子氧下，在溴化物盐和布朗斯台德酸或路易斯酸存在下，由钒催化剂诱导的，与传统的溴化溴化方法相比，该方法提供了一种环保的溴化方法。这种催化反应可以适用于烯烃和炔烃的溴化，得到相应的VIC -溴化物。已证明使用卤化铝代替布朗斯台德酸作为路易斯酸可为氧化溴化提供更实用的方法。从酮中获得α-溴化产物。发现AlBr 3既是溴化物源又是路易斯酸，可以顺利地诱导溴化。511 H NMR实验表明，这种催化溴化反应可能取决于分子氧下钒催化剂的氧化还原循环。
• Iron-Catalyzed Acyl Migration of Tertiary α-Azidyl Ketones: Synthetic Approach toward Enamides and Isoquinolones
  作者：Tonghao Yang、Xing Fan、Xiaopeng Zhao、Wei Yu

  DOI：10.1021/acs.orglett.8b00409

  日期：2018.4.6

  transformed into enamides by treatment with FeBr2 at elevated temperature in DMF. The reaction proceeds via 1,2-benzoyl migration from α-carbon to the nitrogen atom, accompanied by expulsion of a nitrogen molecule. This protocol is suitable for the synthesis of N-(cyclopent-1-en-1-yl)benzamides, N-(cyclohex-1-en-1-yl)benzamides, and N-benzoyl-α-methyl enamines and provides a convenient approach toward isoquinolones

  本文报道，在较高的温度下，通过在DMF中用FeBr 2处理，可以将叔α-叠氮基苯基酮转化为酰胺。该反应通过从α-碳到氮原子的1，2-苯甲酰基迁移而伴随着氮分子的排出而进行。该方案适用于合成N-（环戊-1-烯-1-基）苯甲酰胺，N-（环己-1-烯-1-基）苯甲酰胺和N-苯甲酰基-α-甲基烯胺。异喹诺酮类的简便治疗方法。
• Addition/Cycloaddition of Acetylenedicarboxylates to Open-Chain or Cyclic Amino Carbonyl Compounds
  作者：Giacomo Guerrini、Fabio Ponticelli

  DOI：10.1002/ejoc.201000371

  日期：——

  Some new, interesting, and unknown heterocyclic rings and open-chain molecules have been obtained with ease and under mild conditions by reaction of a wide range of amino carbonyl compounds with acetylenic esters. The reactivity is highly dependent on the substituents and their positions in the starting material, which can be either cyclic (pyrazolones) or open-chain compounds.

  一些新的、有趣的和未知的杂环和开链分子已经通过广泛的氨基羰基化合物与炔酸酯的反应在温和的条件下轻松获得。反应性高度依赖于取代基及其在原料中的位置，原料可以是环状（吡唑啉酮）或开链化合物。
• Reactions of Benzocyclic β-Keto Esters with Sulfonyl Azides. 2.¹ Further Insight into the Influence of Azide Structure and Solvent on the Reaction Course
  作者：Luisa Benati、Daniele Nanni、Piero Spagnolo

  DOI：10.1021/jo9901541

  日期：1999.7.1

  The reactions of 2-ethoxycarbonyl-1-benzosuberone, with 4-methoxybenzenesulfonyl, 2,4,6-triiso-propylbenzenesulfonyl, methanesulfonyl, and trifluoromethanesulfonyl azide, in the presence of triethylamine, have been investigated in N,N-dimethylformamide, acetonitrile, or tetrahydrofuran with the intent of clarifying the influence of both the azide electrophile and solvent on the reaction course. The present findings, in addition to those previously obtained with tosyl and 4-nitrobenzenesulfonyl azide, indicate that both the electronic features of the sulfonyl azide and the solvent polarity greatly affect the possible occurrence of azidation and/or Favorskii-type ring contraction at the expense of deacylating diazo transfer. Azidation is promoted by the less electrophilic azides, while it is virtually avoided by the more electrophilic ones. Ring contraction occurs to a limited extent with the less electrophilic azides, but it becomes the main process with those more electrophilic. Moreover, azidation is virtually unaffected by the solvent polarity, while ring contraction can markedly be enhanced by a highly polar solvent. Firm evidence has additionally been obtained that, in contrast to a previous claim, trifluoromethanesulfonyl azide can normally perform diazotization of acyclic beta-keto esters in preference to azidation.