dimethyl 2-(3-oxo-3-phenylpropyl)malonate | 97427-62-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dimethyl 2-(3-oxo-3-phenylpropyl)malonate
• 英文别名: dimethyl 2-(3-oxo-3-phenylpropyl)propanedioate
• CAS: 97427-62-8
• 化学式: C₁₄H₁₆O₅
• 分子量: 264.278
• InChiKey: NTKVOFSIQDCBAW-UHFFFAOYSA-N

物化性质

• 沸点：
  383.1±32.0 °C(Predicted)
• 密度：
  1.162±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(3-oxo-3-phenylpropyl)malonate 在 乙醚 、 溴 、 sodium methylate 作用下， 生成 2-Benzoyl-1,1-dicarboxy-cyclopropan
  参考文献：
  名称：

  Addition Reactions of Vinyl Phenyl Ketone. III. Methyl Malonate

  摘要：

  DOI：

  10.1021/ja01334a056
• 作为产物：
  描述：

  β-(二甲氨基)苯丙酮 盐酸盐 在 甲醇 、 sodium 作用下， 反应 3.0h， 生成 dimethyl 2-(3-oxo-3-phenylpropyl)malonate
  参考文献：
  名称：

  Crossland, Ingolf; Bock, Klaus; Norrestam, Rolf, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1985, vol. 39, # 1, p. 7 - 14

  摘要：

  DOI：

文献信息

• Cu-Catalyzed Sequential Dehydrogenation–Conjugate Addition for β-Functionalization of Saturated Ketones: Scope and Mechanism
  作者：Xiaoming Jie、Yaping Shang、Xiaofeng Zhang、Weiping Su

  DOI：10.1021/jacs.6b01337

  日期：2016.5.4

  The first copper-catalyzed direct β-functionalization of saturated ketones is reported. This protocol enables diverse ketones to couple with a wide range of nitrogen, oxygen and carbon nucleophiles in generally good yields under operationally simple conditions. The detailed mechanistic studies including kinetic studies, KIE measurements, identification of reaction intermediates, EPR and UV-visible

  报道了第一个铜催化的饱和酮直接β-官能化。该协议使不同的酮能够在操作简单的条件下以通常良好的产率与广泛的氮、氧和碳亲核试剂结合。进行了详细的机理研究，包括动力学研究、KIE 测量、反应中间体的鉴定、EPR 和紫外可见实验，结果表明该反应是通过一种新型的基于自由基的脱氢生成烯酮和随后的共轭加成序列进行的。
• Cooperative Titanocene and Phosphine Catalysis: Accelerated C–X Activation for the Generation of Reactive Organometallics
  作者：Lauren M. Fleury、Andrew D. Kosal、James T. Masters、Brandon L. Ashfeld

  DOI：10.1021/jo301726v

  日期：2013.1.18

  transmetalation approach toward the generation of Grignard and organozinc reagents mediated by a titanocene catalyst. This method enables the metalation of functionalized substrates without loss of functional group compatibility. Allyl zinc reagents and allyl, vinyl, and alkyl Grignard reagents were generated in situ and used in the addition to carbonyl substrates to provide the corresponding carbinols in yields

  本文介绍的研究描述了一种通过钛茂催化剂介导的格氏试剂和有机锌试剂的还原性过渡金属化方法。该方法能够在不损失官能团相容性的情况下金属化官能化的基材。烯丙基锌试剂和烯丙基，乙烯基和烷基格氏试剂原位生成，并用于加成羰基底物，以提供相应的甲醇，收率高达99％。研究发现，膦配体可有效地促进还原性金属转移反应，从而在低至−40°C的温度下实现C–X键的金属化。在手性二胺和氨基醇的存在下进行反应导致醛的对映选择性烯丙基化。
• A new type of δ-vinylvalerolactone for palladium-catalyzed cycloaddition: synthesis of nine-membered heterocycles
  作者：Kuan Li、Sen Yang、Bing Zheng、Wei Wang、Yongjun Wu、Jing Li、Hongchao Guo

  DOI：10.1039/d2cc01134d

  日期：——

  In this paper, a new type of δ-vinylvalerolactone was designed and synthesized, and used as a new precursor in Pd-catalyzed [6+3] cycloaddition with azomethine imines, leading to nine-membered 1,2-dinitrogen-containing heterocycles in 77–98% yields with >20 : 1 d.r. These nine-membered ring-fused products were further transformed into unusual tetracyclic bridged-ring compounds without loss of the

  本文设计合成了一种新型的δ-乙烯基戊内酯，并作为新的前驱体用于Pd催化的[6+3]与偶氮甲亚胺的环加成反应，生成了9元1,2-含二氮杂环。 77–98% 产率，>20 : 1 dr 这些九元环稠合产物进一步转化为不寻常的四环桥环化合物，而不会损失非对映选择性。
• Anodic Cyclization of Dimethyl 2-(3-Oxo-3-arylpropyl) Malonates into the Corresponding Dimethyl 2-Aroylcyclopropane-1,1-dicarboxylates
  作者：Mitsuhiro Okimoto、Haruki Yamamori、Kousuke Ohashi、Masayuki Hoshi、Takashi Yoshida

  DOI：10.1055/s-0033-1339198

  日期：——

  A variety of dimethyl 2-(3-oxo-3-arylpropyl)malonates were electrooxidized in methanol, in the presence of potassium iodide and a base or a neutral salt, to give the corresponding cyclized dimethyl 2-aroylcyclopropane-1,1-dicarboxylates in moderate to good yields. The reactions were carried out under extremely mild reaction conditions, in which the optimal amount of electrolytic current varied from 2.12-2.41 F.mol(-1) depending on the substrates. The reaction presumably proceeds via a two-electron oxidation process, in which iodide ions play an important role as the electron carrier between the anode and the substrate.
• CROSSLAND, I.;BOCK, K.;NORRESTAM, R., ACTA CHEM. SCAND., 1985, 39, N 1, 7-13
  作者：CROSSLAND, I.、BOCK, K.、NORRESTAM, R.

  DOI：——

  日期：——