methyl 3-hydroxy-4-methyl-2-methylenepentanoate | 71385-30-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl 3-hydroxy-4-methyl-2-methylenepentanoate
• 英文别名: Methyl 2-(1-hydroxy-2-methylpropyl)acrylate；methyl 3-hydroxy-4-methyl-2-methylidenepentanoate
• CAS: 71385-30-3
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: GTFGWLIGRMYDJX-UHFFFAOYSA-N

物化性质

• 沸点：
  78-80 °C(Press: 4 Torr)
• 密度：
  1.006±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 3-hydroxy-4-methyl-2-methylenepentanoate 在 indium 、 N-溴代丁二酰亚胺(NBS) 、 二甲基硫 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 20.0h， 生成 methyl 3-(hydroxymethyl)-4-methyl-2-methylenepentanoate
  参考文献：
  名称：

  Effective 1,4-Asymmetric C−C/C−O Stereoinduction in Indium-Promoted Coupling Reactions of Aldehydes to Protected and Unprotected [1-(Bromomethyl)vinyl] Alkanols. The Status of Intramolecular Chelation within Functionalized Allylindium Reagents

  摘要：

  The stereochemistry of the coupling reactions of oxygen-substituted bromides 8-10 with isobutyraldehyde, benzaldehyde, and cyclohexanecarboxaldehyde in water is described. The examples involving the O-silylated derivatives 8 exhibit moderate anti stereoselectivity. In contrast, rather high (most often in excess of 80:20) syn diastereofacial bias is observed when hydroxy bromides 10 are involved. Consequently, stereocontrolled 1,4-asymmetric induction under aqueous conditions can be realized in either direction on demand. These results are considered to reflect the fact that the siloxy systems enter into C-C bond formation via conventional Felkin-Anh transition state arrangements. The crossover observed for the unprotected analogues is believed to be a consequence of the preferred adoption of chelated transition states, these interactions likely being fundamental to aqueous organometallic chemistry.

  DOI：

  10.1021/jo9715534
• 作为产物：
  描述：

  异丁醛 、 丙炔酸甲酯 在 六甲基磷酰三胺 、 二异丁基氢化铝 作用下， 生成 methyl 3-hydroxy-4-methyl-2-methylenepentanoate
  参考文献：
  名称：

  Generation of [.alpha.-(alkoxycarbonyl)vinyl]aluminum and aluminum allenolates by the hydroalumination of .alpha.,.beta.-acetylenic carbonyl compounds and their reaction with carbonyl compounds

  摘要：

  DOI：

  10.1021/jo00240a020

文献信息

• Direct Activation of Unmodified Morita–Baylis–Hillman Alcohols through Phosphine Catalysis for Rapid Construction of Three-Dimensional Heterocyclic Compounds
  作者：Leijie Zhou、Chunhao Yuan、Yuan Zeng、Qijun Wang、Chang Wang、Min Liu、Wei Wang、Yongjun Wu、Bing Zheng、Hongchao Guo

  DOI：10.1021/acs.orglett.9b01783

  日期：2019.6.21

  The phosphine-catalyzed tandem annulation reaction of Morita–Baylis–Hillman (MBH) alcohols with azomethine imines has been achieved for the synthesis of biologically important (epoxymethano)-pyrazolo[5,1-b]quinazoline derivatives. A variety of MBH alcohols and azomethine imines were well-tolerated under the mild reaction conditions, providing novel 3D heterocyclic compounds in high yields with excellent

  Morita–Baylis–Hillman（MBH）醇与偶氮甲亚胺的膦催化串联环化反应已实现，用于合成生物学上重要的（环氧甲氧基）-吡唑并[5,1- b ]喹唑啉衍生物。在温和的反应条件下，多种MBH醇和甲亚胺亚胺具有良好的耐受性，从而以高收率提供了具有出色的非对映选择性的新型3D杂环化合物。这是首次实现了未改性的MBH醇作为新的氧杂合成子的直接活化。
• A chiral squaramide-catalyzed asymmetric dearomative tandem annulation reaction through a kinetic resolution of MBH alcohols: highly enantioselective synthesis of three-dimensional heterocyclic compounds
  作者：Leijie Zhou、Yuan Zeng、Xing Gao、Qijun Wang、Chang Wang、Bo Wang、Wei Wang、Yongjun Wu、Bing Zheng、Hongchao Guo

  DOI：10.1039/c9cc05483a

  日期：——

  dearomative tandem annulation reaction of unmodified Morita–Baylis–Hillman alcohols with azomethine imines has been achieved through a kinetic resolution of MBH alcohols under mild conditions, giving pharmaceutically interesting functionalized hetero-bicyclo[3.3.1]nonane derivatives in good to excellent yields with excellent enantioselectivities.

  在这种交流中，通过温和条件下MBH醇的动力学拆分，实现了未修饰的Morita-Baylis-Hillman醇与偶氮甲亚胺的手性方酸酰胺催化的不对称脱芳香性串联环化反应，得到了药学上有意义的官能化杂双环[3.3.1] ]壬烷衍生物，具有良好的至优异的产率和优异的对映选择性。
• α-Methylene-β-trichloroacetylamino Alkanoates from Trichloroacetimidates of the Baylis-Hillman Adducts
  作者：Mario Orena、Roberta Galeazzi、Gianluca Martelli、Samuele Rinaldi

  DOI：10.1055/s-2004-831235

  日期：——

  The Baylis-Hillman adducts 1 were treated with a large amount of CCl3CN in the presence of DBU without solvent to give in good yield the corresponding trichloroacetimidates 5 which by thermal [3.3]sigmatropic rearrangement were converted into the corresponding (E)-2-trichloroacetylaminomethyl-2-propenoates 6, exclusively. On the contrary, when compounds 5 were treated with a catalytic amount of DABCO in dichloromethane, 2-methylene-3-trichloroacetylamino esters 7 were obtained in good yield. Both 5a and 7a underwent iodocyclization, to give a cyclic intermediate precursor of a polyfunctionalized sequence, and the differences in stereoselectivity were in agreement with computational results.

  Baylis-Hillman加合物1在无溶剂条件下，与大量CCl3CN和DBU反应，以良好产率得到了相应的三氯乙酰亚胺酸酯5，后者通过热[3.3]σ键迁移重排反应，专一性地转化为相应的(E)-2-三氯乙酰胺甲基-2-丙烯酸酯6。相反，当化合物5在二氯甲烷中与少量DABCO反应时，以良好产率得到了2-亚甲基-3-三氯乙酰胺基酯7。无论是5a还是7a，都发生了碘环化反应，得到了多官能团化序列的环状中间体前驱体，其立体选择性的差异与计算结果相符。
• Versatile O- and S-functionalized 1,2,3-triazoliums: ionic liquids for the Baylis–Hillman reaction and ligand precursors for stable MIC-transition metal complexes
  作者：Daniel Mendoza-Espinosa、Rodrigo González-Olvera、Cecilia Osornio、Guillermo E. Negrón-Silva、Rosa Santillan

  DOI：10.1039/c4nj02076f

  日期：——

  A series of O- and S-functionalized triazolium salts display high performance in the Baylis–Hillman addition and allow the one-pot formation of MIC-transition metal complexes.

  一系列的O-和S-官能化三唑盐在Baylis–Hillman加成中表现出高性能，并允许一锅法形成MIC-过渡金属配合物。
• Asymmetric Organocatalysed [1,3]-Sigmatropic Rearrangements
  作者：Sara Kobbelgaard、Sebastian Brandes、Karl Anker Jørgensen

  DOI：10.1002/chem.200701729

  日期：2008.2.8

  The first organocatalysed enantioselective [1,3]-sigmatropic O- to N-rearrangement reactions are presented. The reactions take place under regio- and enantioselective control, and are catalysed by cinchona alkaloids. Two reactions have been developed the first one is the rearrangement of imidates to amides, while the other rearrangement occurs from carbamates to amines via a decarboxylation. Both transformations

  提出了第一个有机催化的对映选择性[1,3]-σO-到N-重排反应。该反应在区域和对映选择性控制下发生，并由金鸡纳生物碱催化。已经开发了两个反应，第一个反应是酰亚胺化为酰胺，而另一个反应是通过脱羧从氨基甲酸酯化为胺。两种转化均得到氮保护的β-氨基酸衍生物作为产物。这些新颖的不对称有机催化的[1,3]-σO-N重排反应为从外消旋起始原料中以高收率获得对映体富集的β-氨基酸衍生物提供了可靠而有效的合成方法。