methyl 3-(4-bromophenyl)-2-methyl-3-oxopropanoate | 86109-33-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-(4-bromophenyl)-2-methyl-3-oxopropanoate
• CAS: 86109-33-3
• 化学式: C₁₁H₁₁BrO₃
• 分子量: 271.111
• InChiKey: SJNKCXUZLSQFME-UHFFFAOYSA-N

物化性质

• 沸点：
  325.9±22.0 °C(Predicted)
• 密度：
  1.422±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  methyl 3-(4-bromophenyl)-2-methyl-3-oxopropanoate 在 盐酸羟胺 、 sodium acetate 作用下， 以 乙醇 为溶剂， 以0.5417 g的产率得到3-(4-bromophenyl)-4-methylisoxazol-5(4H)-one
  参考文献：
  名称：

  异恶唑酮与异氰酸酯的钯催化扩环反应：1,3-氧杂嗪-6-一衍生物的合成

  摘要：

  公开了异恶唑酮与异氰酸酯的钯催化的扩环反应。在反应中，提出了涉及开环/环化的级联过程。该反应由于没有消除CO 2而具有高原子经济性。此外，所获得的产品展示出具有较高固态发射效率的聚集诱发的发射特性。

  DOI：

  10.1002/adsc.202001200
• 作为产物：
  描述：

  2-[(4-bromo-phenyl)-hydroxy-methyl]-acrylic acid methyl ester 在 2-碘酰基苯甲酸 作用下， 以 乙醇 、 水 、 乙腈 为溶剂， 反应 144.0h， 生成 methyl 3-(4-bromophenyl)-2-methyl-3-oxopropanoate
  参考文献：
  名称：

  Regio- and enantioselective bioreduction of methyleneketoesters using both polymeric resin and cellulose matrix

  摘要：

  Methyleneketoesters were prepared in >90% yield by performing an IBX oxidation of Morita-Baylis-Hillman adducts. A methodology was developed to achieve methyl 3-aryl-3-keto-2-methylenepropanoate reduction using a screening of yeast strains in three different reaction procedures to obtain products with both high yield and diastereoselectivity. The reactions conducted in water provided inferior yields (50%) for substrates 2b-c. Employing Amberlite (R) XAD7HP which was a substrate reservoir that also immediately extracted the products from the reaction medium after their formation, syn-4a-c and anti-4a-c were isolated in 60-70% yield, with high stereoselectivity (98-99% ee). The best results were obtained using substrates adsorbed on filter paper which provided products yields above 70%, a 99% ee and a diastereomoeric ratio (syn-4: anti-4) 9:1. Cellulose matrix has excellent potential to be successfully employed in general biocatalytic reactions. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2013.09.018

文献信息

• Iron-catalysed 1,2-acyl migration of tertiary α-azido ketones and 2-azido-1,3-dicarbonyl compounds
  作者：Tonghao Yang、Yajun Lin、Chaoqun Yang、Wei Yu

  DOI：10.1039/c9gc02085c

  日期：——

  Iron-catalysed 1,2-acyl migration of tertiary α-azido ketones and 2-azido-1,3-dicarbonyl compounds provides a simple and atom-economical approach toward enamides and isoquinolones. This paper reports two catalyst systems for these transformations which employ iron(II) complexes [Fe(dpbz)]Br2 (dpbz = 1,2-bis(diphenylphosphino)benzene) and FeBr2/Et3N, respectively. [Fe(dpbz)]Br2 was found to be highly

  铁催化的α-叠氮基酮和2-叠氮基-1,3-二羰基化合物的1,2-酰基迁移为酰胺和异喹啉酮提供了一种简单且原子经济的方法。本文报道两种催化剂体系用于这些转化其采用铁（II）配合物的[Fe（dpbz）]溴2（dpbz = 1,2-双（二苯基膦基）苯）和FeBr 2 / ET 3 N，分别。发现[Fe（dpbz）] Br 2在将2-叠氮基-2,3-二氢-1 H-茚满-1-酮转化为异喹诺酮方面非常有效。另一方面，由于Et 3的有益作用，FeBr 2 / Et 3 N的试剂组合具有更宽的催化范围N.后一种催化剂体系可使2-叠氮基-2-甲基-1,3-二羰基化合物在温和条件下以良好的收率转化为相应的酰胺。
• Enantio-, Diastereo-, and Regioselective Iridium-Catalyzed Asymmetric Allylic Alkylation of Acyclic β-Ketoesters
  作者：Wen-Bo Liu、Corey M. Reeves、Brian M. Stoltz

  DOI：10.1021/ja4097829

  日期：2013.11.20

  The first regio-, diastereo-, and enantioselective allylic alkylation of acyclic β-ketoesters to form vicinal tertiary and all-carbon quaternary stereocenters is reported. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands. Broad functional group tolerance is observed at the keto-, ester-, and α-positions of the

  报道了第一个区域选择性、非对映选择性和对映选择性烯丙基烷基化无环 β-酮酯以形成邻位叔和全碳四元立体中心。该方法成功开发的关键是使用铱催化与 N-芳基亚磷酰胺配体。在亲核试剂的酮-、酯-和α-位观察到广泛的官能团耐受性。各种转换证明了该方法可用于快速访问复杂的对映体富集化合物。
• Sterically Hindered Chiral Ferrocenyl P,N,N-Ligands for Highly Diastereo-/Enantioselective Ir-Catalyzed Hydrogenation of α-Alkyl-β-ketoesters via Dynamic Kinetic Resolution
  作者：Chuan-Jin Hou、Xiang-Ping Hu

  DOI：10.1021/acs.orglett.6b02828

  日期：2016.11.4

  A new class of sterically hindered chiral ferrocenyl P,N,N-ligands have been prepared through a two-step transformation from (Sc,Rp)-PPFNH2, in which a new (R)-stereogenic center at the pyridinylmethyl position was generated in high diastereoselectivity. With these newly developed P,N,N-ligands, Ir-catalyzed asymmetric hydrogenation of various α-alkyl-substituted β-aryl-β-ketoesters via dynamic kinetic

  通过从（S c，R p）-PPFNH 2的两步转化制备了新型的空间位阻性手性二茂铁基二茂铁基P，N，N-配体，其中在吡啶基甲基位置上有一个新的（R）-立体异构中心产生的非对映异构体选择性高。借助这些新开发的P，N，N配体，首次在高非对映体和对映体选择性下，通过动态动力学拆分实现了Ir催化的各种α-烷基取代的β-芳基-β-酮酸酯的不对称氢化，导致了多种光学活性的反-β-羟基酯含量高达99％ee。研究表明，这些配体的吡啶基甲基位置上的额外立体中心对于实现这种氢化作用至关重要。
• Azidation of β-Keto Esters and Silyl Enol Ethers with a Benziodoxole Reagent
  作者：Maria Victoria Vita、Jérôme Waser

  DOI：10.1021/ol401229v

  日期：2013.7.5

  The efficient azidation of β-keto esters and silyl enol ethers using a benziodoxole-derived azide transfer reagent is reported. The azidation of cyclic β-keto esters could be achieved in up to quantitative yields in the absence of any catalyst. In the case of less reactive linear β-keto esters and silyl enol ethers, complete conversion and good yields could be obtained by using a zinc catalyst.

  据报道，使用苯并恶二唑衍生的叠氮化物转移试剂可有效地叠氮化β-酮酯和甲硅烷基烯醇醚。在不存在任何催化剂的情况下，可以高达定量的产率实现环状β-酮酯的叠氮化。在反应性较低的线性β-酮酯和甲硅烷基烯醇醚的情况下，通过使用锌催化剂可以获得完全的转化和良好的产率。
• Palladium-Catalyzed Carbonylation/Acyl Migratory Insertion Sequence
  作者：Zhenhua Zhang、Yiyang Liu、Mingxing Gong、Xiaokun Zhao、Yan Zhang、Jianbo Wang

  DOI：10.1002/anie.200906349

  日期：2010.2.1

  On the move: A palladium‐catalyzed reaction of aryl iodides, diazo compounds or N‐tosylhydrazones, and carbon monoxide affords β‐oxo esters or ketones/enones (see scheme; DCE=1,2‐dichloroethane). The products are delivered with high efficiency through the title sequence.

  进展中：芳基碘化物，重氮化合物或N-甲苯磺酰hydr与一氧化碳的钯催化反应可制得β-氧代酯或酮/烯酮（参见方案； DCE = 1,2-二氯乙烷）。产品通过标题顺序高效交付。