3-(4-bromophenyl)-2-methyl-3-oxopropionic acid ethyl ester | 52884-49-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(4-bromophenyl)-2-methyl-3-oxopropionic acid ethyl ester
• 英文别名: 3-(p-bromophenyl)-2-methyl-3-oxopropionic acid ethyl ester；Ethyl-α-methyl-p-brombenzoylacetat；ethyl 3-(4-bromophenyl)-2-methyl-3-oxopropanoate
• CAS: 52884-49-8
• 化学式: C₁₂H₁₃BrO₃
• 分子量: 285.137
• InChiKey: SQRBZNPSXBLVEQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 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

安全信息

• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P340,P330,P363,P501
• 危险性描述：
  H302,H312,H332

反应信息

• 作为反应物：
  描述：

  3-(4-bromophenyl)-2-methyl-3-oxopropionic acid ethyl ester 在 5 5'-二甲基-2,2'-二吡啶 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 盐酸羟胺 、 sodium acetate 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 、 水 、 甲苯 、 mineral oil 为溶剂， 反应 111.5h， 生成 2-(4-bromophenyl)-3-methyl-5-phenylpyridine
  参考文献：
  名称：

  钌催化脱羧和脱氢形成烯烃系异恶唑-5(4H)-酮高度取代的吡啶

  摘要：

  已经开发了一种钌催化的烯烃系异恶唑-5(4H)-酮反应生成吡啶。从各种异恶唑酮中获得二、三和四取代的吡啶...

  DOI：

  10.1246/cl.160480
• 作为产物：
  描述：

  碘甲烷 、 (4-溴苯甲酰)乙酸乙酯 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 3-(4-bromophenyl)-2-methyl-3-oxopropionic acid ethyl ester
  参考文献：
  名称：

  Copper(II) Triflate Catalyzed Amination and Aziridination of 2-Alkyl Substituted 1,3-Dicarbonyl Compounds

  摘要：

  A method to prepare alpha-acyl-beta-amino acid and 2,2-diacyl aziridine derivatives efficiently from Cu(OTf)(2) + 1,10-phenanthroline (1,10-phen)-catalyzed amination and aziridination of 2-alkyl substituted 1,3-dicarbonyl compounds with PhI=NTs is described. By taking advantage of the orthogonal modes of reactivity of the substrate through slight modification of the reaction conditions, a divergence in product selectivity was observed. In the presence of 1.2 equiv of the iminoiodane, amination of the allylic C-H bond of the enolic form of the substrate, formed in situ through coordination to the Lewis acidic metal catalyst, was found to selectively occur and give the beta-aminatecl adduct. On the other hand, increasing the amount of the nitrogen source from 1.2 to 2-3 equiv was discovered to result in preferential formal aziridination of the C-C bond of the 2-alkyl substituent of the starting material and formation of the aziridine product.

  DOI：

  10.1021/ja301415k

文献信息

• Enantioselective Borohydride Reduction Catalyzed by Optically Active Cobalt Complexes
  作者：Tohru Yamada、Takushi Nagata、Kiyoaki D. Sugi、Kiyotaka Yorozu、Taketo Ikeno、Yuhki Ohtsuka、Daichi Miyazaki、Teruaki Mukaiyama

  DOI：10.1002/chem.200304794

  日期：2003.9.22

  enantioselective borohydride reduction of aromatic ketones or imines to the corresponding alcohols was developed in the presence of a catalytic amount of an optically active cobalt(II) complex catalyst. This enantioselective reduction is carried out using a precisely premodified borohydride with alcohols such as tetrahydrofurfuryl alcohol, ethanol and methanol. High optical yields are obtained by choosing

  在催化量的光学活性钴（II）络合物催化剂的存在下，芳香族酮或亚胺对映体的高度对映选择性硼氢化物还原。该对映选择性还原是使用精确预改性的硼氢化物与醇（例如四氢糠醇，乙醇和甲醇）进行的。通过选择合适的醇作为改性剂和合适的催化剂β-酮亚氨基配体，可以获得高的光学收率。对映选择性硼氢化物还原已成功应用于光学活性的1,3-二醇的制备，双酰基二茂铁的立体选择性还原以及1,3-二羰基化合物的动态和/或动力学拆分。
• Dynamic Kinetic Resolution with Enantioselective Borohydride Reduction Catalyzed by Optically Active β-Ketoiminato Cobalt(II) Complexes: Highly Diastereo- and Enantioselective Preparation of Optically Active<i>anti</i>-Aldol Compounds
  作者：Yuhki Ohtsuka、Daichi Miyazaki、Taketo Ikeno、Tohru Yamada

  DOI：10.1246/cl.2002.24

  日期：2002.1

  Optically active anti-2-alkyl-3-hydroxy esters were stereoselectively obtained from the corresponding 2-alkyl-3-keto esters using enantioselective borohydride reduction along with dynamic kinetic resolution in the presence of optically active β-ketoiminato cobalt complex catalysts. The reduction system provided an alternative preparation for anti-aldol compounds with high diastereo- and enantioselectivities

  在光学活性β-酮亚氨基钴配合物催化剂存在下，使用对映选择性硼氢化物还原以及动态动力学拆分，从相应的2-烷基-3-酮酯立体选择性地获得了光学活性的抗2-烷基-3-羟基酯。该还原系统为具有高非对映选择性和对映选择性的抗羟醛化合物提供了另一种制备方法。
• Electrophilic α-Amination Reaction of β-Ketoesters Using <i>N</i>-Hydroxycarbamates: Merging Aerobic Oxidation and Lewis Acid Catalysis
  作者：David Sandoval、Charles P. Frazier、Alejandro Bugarin、Javier Read de Alaniz

  DOI：10.1021/ja310784f

  日期：2012.11.21

  The copper-catalyzed α-amination of carbonyl compounds using nitrosoformate intermediates as the electrophilic source of nitrogen is reported. The reaction merges aerobic oxidation and Lewis acid catalysis. The scope of the reaction is broad in terms of both the N-substituted hydroxylamines and the β-ketoesters. The new methodology harnesses the power of nitrosoformate intermediates and demonstrates

  报道了使用亚硝基甲酸酯中间体作为氮的亲电子源的羰基化合物的铜催化α-胺化。该反应结合了好氧氧化和路易斯酸催化。就 N-取代的羟胺和 β-酮酯而言，该反应的范围很广。新方法利用亚硝基甲酸酯中间体的力量，并展示了它们作为 α-官能化反应中可行的亲电氮源的潜力。
• Pharmaceutical substituted propanoic acid derivatives
  申请人：ELI LILLY AND COMPANY LIMITED

  公开号：EP0849263A2

  公开（公告）日：1998-06-24

  A pharmaceutical compound of the formula: in which A is carboxy, tetrazolyl, -SO2H, -SO3H, -OSO3H, -CONHOH, or -P(OH)OR', -PO(OH)OR', -OPO(OH)OR' where R' is hydrogen, C1-6 alkyl, C2-6 alkenyl or optionally substituted phenyl-C1-6 alkyl, B is a bond, C1-6 alkylene or C2-6 alkenylene, R1 is hydrogen, hydroxyl, halo or group of the formula A-B-, X is C1-6 alkylene, C2-6 alkenylene, C2-6 alkynylene or C1-6 alkylene linked through -O-, -S- or -NR"- to Y, where R" is hydrogen or C1-6 alkyl, and Y is (1) in which R2 and R3 are each halo, nitro, nitrile, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl or optionally substituted phenyl, m and n are each 0 to 3, Q is -O-, -S-, -SO-, -SO2-, -CH=CH-, -(CH2)p-,-CONR"'- or -NR"'CO-, where p is 0 to 3 and R"' is hydrogen or C1-6 alkyl, and Z is or (2) in which R2, R3, m, n and Z are as defined above; provided that when Z is X is C1-6 alkylene, C2-6 alkenylene or C2-6 alkynylene; and salts and esters thereof.

  式的药物化合物： 其中 A 是羧基、四唑基、-SO2H、-SO3H、-OSO3H、-CONHOH 或-P(OH)OR'、-PO(OH)OR'、-OPO(OH)OR'，其中 R' 是氢、C1-6 烷基、C2-6 烯基或任选取代的苯基-C1-6 烷基、 B 是键、C1-6 烯基或 C2-6 烯基、 R1 是氢、羟基、卤代或式 A-B- 的基团、 X 是通过 -O-、-S- 或 -NR"- 与 Y 连接的 C1-6 亚烷基、C2-6 亚烯基、C2-6 亚炔基或 C1-6 亚烷基，其中 R" 是氢或 C1-6 烷基、 而 Y 是 (1) 其中 R2 和 R3 分别为卤代、硝基、腈基、C1-6 烷基、C2-6 烯基、C2-6 炔基或任选取代的苯基，m 和 n 分别为 0 至 3，Q 为-O-、-S-、-SO-、-SO2-、-CH=CH-、-(CH2)p-、-CONR"'- 或-NR"'CO-，其中 p 为 0 至 3，R"'为氢或 C1-6 烷基，且 Z 为 或 (2) 其中 R2、R3、m、n 和 Z 如上定义； 但当 Z 为 X 为 C1-6 亚烷基、C2-6 亚烯基或 C2-6 亚炔基； 及其盐类和酯类。
• Iron-Catalyzed Oxidative C–C and C–O Coupling of Halophenols to α-Substituted β-Keto Esters
  作者：Doron Pappo、Almog Regev、Hadas Shalit

  DOI：10.1055/s-0034-1380360

  日期：——

  The iron-catalyzed oxidative cross-coupling of halophenols to -substituted -keto esters takes place through one of two modes: oxidative C-C coupling or oxidative C-O coupling. A mechanistic investigation revealed that the chemoselectivity of these reactions is determined by the electronic and steric properties of the two coupling partners.