1-methyl-1-phenylethyl 3-oxobutyrate | 91328-34-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-methyl-1-phenylethyl 3-oxobutyrate
• 英文别名: 2-phenylpropan-2-yl 3-oxobutanoate；1-methyl-1-phenylethyl 3-oxobutanoate；2-phenyl-2-propyl acetoacetate
• CAS: 91328-34-6
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: GMWRLZCGZFSPCW-UHFFFAOYSA-N

物化性质

• 沸点：
  301.3±17.0 °C(Predicted)
• 密度：
  1.067±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  1-methyl-1-phenylethyl 3-oxobutyrate 在 氢氧化钾 、 sodium hydride 作用下， 以 乙醇 、 水 为溶剂， 反应 64.0h， 生成 2-Hydroxymethyl-2-methyl-3-oxo-butyric acid 1-methyl-1-phenyl-ethyl ester
  参考文献：
  名称：

  Autocatalytic Fragmentation of Acetoacetate Derivatives as Acid Amplifiers to Proliferate Acid Molecules

  摘要：

  A novel concept of acid proliferation to improve the photosensitivity of chemically amplified photoresist materials is described by presenting the autocatalytic fragmentation of acetoacetates having a (sulfonyloxy)methyl residue to liberate the corresponding sulfonic acid. 2-Methyl-2-((methane-or p-toluenesulfonyloxy)methyl) acetoacetates were designed to be subjected to the acid-catalyzed fragmentation through the corresponding acetoacetic acids which are readily decarboxylated and undergo the subsequent beta-elimination to give a sulfonic acid which can act as the autocatalyst to lead to the increment of acid concentration in geometric progression. Among the acetoacetates tested, tert-butyl 2-methyl-2-((p-toluenesulfonyloxy)methyl)acetoacetate was the most suitable reagent for the present purpose because of its reasonable thermal stability. A nonlinear generation of the sulfonic acid was confirmed in the acidolytic transformation of the acetoacetate in nonpolar solvents and in a film of poly [4-((tert-butoxycarbonyl) oxy)styrene] (PBOCSt), respectively. It was found that the addition of the acetoacetate to a film of PBOCSt doped with a photoacid generator enhances the photosensitivity characteristics.

  DOI：

  10.1021/ja972353c
• 作为产物：
  描述：

  2-苯基-2-丙醇 、 乙酰乙酸甲酯 在 sodium acetate 作用下， 以 甲苯 为溶剂， 以93%的产率得到1-methyl-1-phenylethyl 3-oxobutyrate
  参考文献：
  名称：

  2-重氮-3-氧代-6-庚烯酸酯的催化不对称分子内环丙烷化

  摘要：

  本手稿描述了对 2-重氮-3-氧代-6-庚烯酸酯的催化不对称分子内环丙烷化 (IMCP) 的研究。对映选择性取决于酯部分的体积，2-diazo-3-oxo-6-heptenoic 酸的 2,6-二叔丁基-4-甲基苯基酯为产物提供 78% ee，表明α-重氮-β-酮酯的催化不对称 IMCP 可能是天然产物和人工分子的对映选择性合成的关键反应。

  DOI：

  10.1055/s-2007-967964

文献信息

• Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds
  作者：Durga Prasad Hari、Jerome Waser

  DOI：10.1021/jacs.7b04756

  日期：2017.6.28

  Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks

  允许将亲核试剂和亲电试剂添加到重氮化合物上的对映选择性催化方法可以快速进入重要的构建模块。在此，我们报告了使用乙炔基苯并氧醇-(on)e 试剂和简单的铜双恶唑啉催化剂对重氮化合物进行高度对映选择性的氧炔基化反应。获得的α-苯甲酰氧基炔丙酯是有用的结构单元，使用其他方法难以以对映体纯形式合成。所得产物可以有效地转化为邻二醇和α-羟基炔丙酯而不会损失对映体纯度。
• Ru(<scp>ii</scp>)-Pheox-catalyzed Si–H insertion reaction: construction of enantioenriched carbon and silicon centers
  作者：Yoko Nakagawa、Soda Chanthamath、Ikuhide Fujisawa、Kazutaka Shibatomi、Seiji Iwasa

  DOI：10.1039/c7cc01070b

  日期：——

  We established a highly enantioselective Si-H insertion reaction to construct chiral centers at the carbon and silicon atoms, using Ru(II)-Pheox catalyst. The catalytic asymmetric Si-H insertion reaction of [small alpha]-methyl-[small alpha]-diazoesters proceeded...

  我们建立了一个高度对映选择性的Si-H插入反应，使用Ru（II）-Pheox催化剂在碳和硅原子上构建了手性中心。[小α]-甲基-[小α]-重氮酯的催化不对称Si-H插入反应进行...
• Asymmetric Catalysis on the Intramolecular Cyclopropanation of α-Diazo-β-keto Sulfones
  作者：Masahiro Honma、Takashi Sawada、Yuri Fujisawa、Masayuki Utsugi、Hideaki Watanabe、Akinori Umino、Takehiko Matsumura、Takayuki Hagihara、Masashi Takano、Masahisa Nakada

  DOI：10.1021/ja029534l

  日期：2003.3.1

  analysis, and the outcome of the enantioselectivities is explained well by our proposed models A and B. The products possess great potential for natural product synthesis because (1) many different chemistries of cyclopropane, ketone, and sulfone are available, and (2) the products are generally highly crystalline, facilitating the supplies of enantiomerically pure synthetic intermediates.

  这项工作描述了对 α-重氮-β-酮砜的分子内环丙烷化的高度对映选择性不对称催化的发展。我们发现，当 α-重氮-β-酮基甲基砜与新制备的配体 2e 一起使用时，α-重氮-β-酮基砜的催化不对称分子内反应通常以高对映选择性进行。产品的绝对构型已通过 X 射线晶体学分析确定，我们提出的模型 A 和 B 很好地解释了对映选择性的结果。这些产品具有天然产物合成的巨大潜力，因为 (1) 环丙烷的许多不同化学性质、酮、砜都有，（2）产物一般是高度结晶的，
• Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds
  作者：Durga Prasad Hari、Lionel Schouwey、Verity Barber、Rosario Scopelliti、Farzaneh Fadaei‐Tirani、Jerome Waser

  DOI：10.1002/chem.201900950

  日期：2019.7.17

  radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine‐tuning of the reagent structure and reactivity. EBZ reagents

  乙炔基苯并恶唑（EBX）环状高价碘试剂现已确立为自由基和亲核试剂烷基化的试剂，但它们为进一步的结构和反应性修饰提供了有限的可能性。在此，报道了相应乙炔基苯并偶氮酮（EBZ）试剂的第一次合成，其中碘杂环中的氧原子被氮原子取代。氮上的取代基可进一步微调试剂的结构和反应性。EBZ试剂可通过一步步骤轻松地从相应的苯甲酰胺中获得，并具有与EBX试剂相当的反应性。特别是，它们被用于重氮化合物的不对称铜催化的氧炔基化反应中，
• NEW ANALOGS AS ANDROGEN RECEPTOR AND GLUCOCORTICOID RECEPTOR MODULATORS
  申请人：Oncostellae, S.L.

  公开号：EP3480201A1

  公开（公告）日：2019-05-08

  The present invention relates to novel dihydropyridine derivatives of formula (I): as modulators of nuclear receptors selected from androgen receptor and glucocorticoid receptor, to processes for their preparation, to pharmaceutical compositions comprising said compounds and to the use of said for manufacturing a medicament for the treatment of pathological conditions or diseases that can improve by modulation of androgen receptor and/or glucocorticoid receptor, selected from cancer, metastasizing cancers, benign prostate hyperplasia, polycystic ovary syndrome (PCOS), hair loss, hirsutism, acne, hypogonadism, muscle wasting diseases, cachexia, Cushing's syndrome, anti-psychotic drug induced weight gain, obesity, post-traumatic stress disorder and alcoholism.

  本发明涉及一种新型的二氢吡啶衍生物，其化学式为(I)：作为选择的核受体调节剂，所述核受体包括雄激素受体和糖皮质激素受体，以及其制备方法，包括所述化合物的制药组合物和利用所述化合物制造用于治疗可以通过调节雄激素受体和/或糖皮质激素受体改善的病理情况或疾病的药物，所述病理情况或疾病包括癌症、转移性癌症、良性前列腺增生、多囊卵巢综合征（PCOS）、脱发、多毛症、痤疮、性腺功能减退、肌肉消耗性疾病、虚弱、库欣综合征、抗精神病药物诱导的体重增加、肥胖、创伤后应激障碍和酗酒。