tert-butyl 3-hydroxy-2-methylenebutanoate | 135507-83-4

• 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: tert-butyl 3-hydroxy-2-methylenebutanoate
• 英文别名: Butanoic acid, 3-hydroxy-2-methylene-, 1,1-dimethylethyl ester；tert-butyl 3-hydroxy-2-methylidenebutanoate
• CAS: 135507-83-4；87102-04-3
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: PEAMXOGDUHURCZ-UHFFFAOYSA-N

物化性质

• 沸点：
  235.7±23.0 °C(Predicted)
• 密度：
  0.993±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  tert-butyl 3-hydroxy-2-methylenebutanoate 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4 A molecular sieve 作用下， 以 异辛烷 、 二氯甲烷 为溶剂， 以78%的产率得到tert-butyl syn-2-methylene epoxy-3-hydroxybutanoate
  参考文献：
  名称：

  Asymmetric metal-catalysed epoxidation of electron-deficient olefins

  摘要：

  The SYN diastereospecific epoxidation of acyclic beta-hydroxyketones (beta-hydroxyacrylates) and cyclic beta-hydroxyketones using titanium and vanadium catalysts is reported. Some initial results on the asymmetric epoxidation of these systems using the Sharpless titanium-tartrate catalyst are also described.

  DOI：

  10.1016/s0957-4166(00)86103-0
• 作为产物：
  描述：

  丙烯酸叔丁酯 、 乙醛 在 三乙烯二胺 作用下， 反应 168.0h， 以92%的产率得到tert-butyl 3-hydroxy-2-methylenebutanoate
  参考文献：
  名称：

  1,4-重氮双环[2.2.2]辛烷催化的醛与活化双键偶联。第3部分。短时实用合成麦卡尼克酸（4-乙烯基-1-环己烯-1,4-二羧酸）†

  摘要：

  通过1，4-二氮杂双环[2.2.2]辛烷（DABCO）催化的乙醛和丙酸叔丁酯（3）到4，S N 2'-的偶联，以24％的总收率制备了标题二羧酸1d。反应到叔丁基（ż）-2- romomethyl -2-丁烯酸甲酯（图5a），dehydrobrominatin到叔丁基2-亚甲基-3-丁烯酸乙酯（2C），dimerizatoin到二-叔丁基4-乙烯基-1-环己烯-1，4-二羧酸酯（1c）和酸性酯裂解。易裂解5a的酸性裂解相对于乙醛，以68％的收率得到（Z）-2-溴甲基-2-丁烯酸（5a）。

  DOI：

  10.1002/hlca.19840670209

文献信息

• Palladium-Catalyzed Direct Intramolecular C–N Bond Formation: Access to Multisubstituted Dihydropyrroles
  作者：Bing Jiang、Fei-Fan Meng、Qiu-Ju Liang、Yun-He Xu、Teck-Peng Loh

  DOI：10.1021/acs.orglett.7b00072

  日期：2017.2.17

  A palladium-catalyzed intramolecular amination of alkenes with retention of olefin functionalization was achieved under mild reaction conditions. In the presence of palladium catalyst, the tosyl-protected amine can directly couple with a double bond to provide versatile dihydropyrrole derivatives in moderate to excellent yields.

  在温和的反应条件下，实现了钯催化的烯烃分子内胺化反应，同时保留了烯烃的官能团。在钯催化剂的存在下，甲苯磺酰基保护的胺可以直接与双键偶联，以中等至优异的产率提供通用的二氢吡咯衍生物。
• Divergent Amine-Catalyzed [4 + 2] Annulation of Morita–Baylis–Hillman Allylic Acetates with Electron-Deficient Alkenes
  作者：Silong Xu、Rongshun Chen、Zifeng Qin、Guiping Wu、Zhengjie He

  DOI：10.1021/ol2032569

  日期：2012.2.17

  + 2] annulation of Morita–Baylis–Hillman allylic acetates 2 with electron-deficient alkenes or diazenes has been developed for efficient syntheses of highly functionalized cyclohexenes, tetrahydropyridazines, and important spirocycles. This reaction unveils a new reactivity pattern of the intensely studied allylic compounds 2 acting as a C4 synthon in Lewis base catalyzed annulation reactions and also

  已开发出一种胺催化的Morita-Baylis-Hillman烯丙基乙酸2与电子缺陷的烯或二氮烯环化的[4 + 2]环，可高效合成高度官能化的环己烯，四氢哒嗪和重要的螺环。该反应揭示了在Lewis碱催化的环化反应中被大量研究的烯丙基化合物2作为C 4合成子的新反应模式，并且还展示了叔胺和膦之间的发散催化作用。
• 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。
• Acyclic Stereocontrol of Free Radical Reactions Involving Alkyl 2-(1-Hydroxyalkyl)propenoates
  作者：FW Eastwood、RD Mifsud、P Perlmutter

  DOI：10.1071/ch9942187

  日期：——

  The addition of cyclohexyl and t-butyl free radicals to silylated derivatives of alkyl 2-(1-hydroxyalkyl) propenoates was found to be stereoselective . In the case of the cyclohexyl radical the stereoselectivity was dependent upon the conditions used to generate the free radical and to quench the intermediate. Stereoselectivity in additions of the t-butyl radical was found to be temperature-dependent. In all cases stereoselectivity increased as the steric bulk of the group attached to the carbinol oxygen increased. A simple model which accounts for the stereoselectivity is proposed.

  研究发现，环己基和叔丁基自由基与 2-（1-羟基烷基）丙烯酸烷基硅烷化衍生物的加成具有立体选择性。环己基自由基的立体选择性取决于生成自由基和淬灭中间体的条件。研究发现，t-丁基自由基加成的立体选择性与温度有关。在所有情况下，立体选择性都会随着连接到羰基氧上的基团立体体积的增加而增加。提出了一个解释立体选择性的简单模型。
• 1,4-Diazobicyclo[2.2.2]octane-catalyzed coupling of aldehydes and activated double bonds. Part 3. A short ans practical synthesis of mikanecic acid (4-vinyl-1-cyclohexene-1,4-dicarboxylic acid)
  作者：H. M. R. Hoffmann、J�rgen Rabe

  DOI：10.1002/hlca.19840670209

  日期：1984.3.14

  in 24% overall yield via, 1,4-diazabicyclo[2.2.2]octane (DABCO)-catalyzed coupling of ethanal and tert-butyl propenoate (3) to 4, SN2′-reaction to tert-butyl (Z)-2-romomethyl-2-butenoate (5a), dehydrobrominatin to tert-butyl 2-methylidene-3-butenoate (2c), dimerizatoin to di-tert-butyl 4-vinyl-1-cyclohexene-1,4-dicarboxylate (1c) and acidic ester cleavage. Acidic cleavage of easily obtainable 5a affords

  通过1，4-二氮杂双环[2.2.2]辛烷（DABCO）催化的乙醛和丙酸叔丁酯（3）到4，S N 2'-的偶联，以24％的总收率制备了标题二羧酸1d。反应到叔丁基（ż）-2- romomethyl -2-丁烯酸甲酯（图5a），dehydrobrominatin到叔丁基2-亚甲基-3-丁烯酸乙酯（2C），dimerizatoin到二-叔丁基4-乙烯基-1-环己烯-1，4-二羧酸酯（1c）和酸性酯裂解。易裂解5a的酸性裂解相对于乙醛，以68％的收率得到（Z）-2-溴甲基-2-丁烯酸（5a）。