tert-butyl 3-acetoxy-2-methylenebutanoate | 927408-60-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: tert-butyl 3-acetoxy-2-methylenebutanoate
• 英文别名: Tert-butyl 3-acetyloxy-2-methylidenebutanoate
• CAS: 927408-60-4
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: SXOPXTQTEIKMPS-UHFFFAOYSA-N

物化性质

• 沸点：
  269.1±23.0 °C(Predicted)
• 密度：
  1.008±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl 3-acetoxy-2-methylenebutanoate 在 (R)-Cl-MeO-BIPHEP-Ru 苯磺酰胺 、 氢气 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 0.25h， 生成 methyl 2-(S)-[(dimethylphosphoryl)methyl]-butanoate
  参考文献：
  名称：

  Asymmetric Synthesis of 2-Alkyl-3-phosphonopropanoic Acids via P−C Bond Formation and Hydrogenation

  摘要：

  Allylic acetates, formed by the acetylation of Baylis Hillman adducts, undergo addition of phosphorus nucleophiles to give stereoselectively the Z-unsaturated esters. TFA cleavage of the tert-butyl ester and asymmetric hydrogenation of the unsaturated acid yields the phosphono alkyl propanoic acid moiety, commonly found in phosphonate- and phosphinate-based enzyme inhibitors.

  DOI：

  10.1021/ol701500s
• 作为产物：
  描述：

  丙烯酸叔丁酯 在 吡啶 、 三乙烯二胺 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 23.0h， 生成 tert-butyl 3-acetoxy-2-methylenebutanoate
  参考文献：
  名称：

  Asymmetric Synthesis of 2-Alkyl-3-phosphonopropanoic Acids via P−C Bond Formation and Hydrogenation

  摘要：

  Allylic acetates, formed by the acetylation of Baylis Hillman adducts, undergo addition of phosphorus nucleophiles to give stereoselectively the Z-unsaturated esters. TFA cleavage of the tert-butyl ester and asymmetric hydrogenation of the unsaturated acid yields the phosphono alkyl propanoic acid moiety, commonly found in phosphonate- and phosphinate-based enzyme inhibitors.

  DOI：

  10.1021/ol701500s

文献信息

• 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。
• Construction of dispirocyclohexanes via amine-catalyzed [2 + 2 + 2] annulations of Morita–Baylis–Hillman acetates with exocyclic alkenes
  作者：Rongshun Chen、Silong Xu、Xia Fan、Hanyuan Li、Yuhai Tang、Zhengjie He

  DOI：10.1039/c4ob01927j

  日期：——

  Amine-catalyzed [2 + 2 + 2] annulations of one molecule of Morita–Baylis–Hillman (MBH) acetates 1 with two molecules of 2-(arylmethylidene)indane-1,3-diones 2 or methyleneindolinones 4 have been developed under very mild conditions, which produce multistereogenic dispirocyclohexanes 3 and 5, respectively, in moderate to excellent yields and good diastereoselectivity. This amine-catalyzed annulation constitutes

  胺催化的[2 + 2 + 2]森田-的Baylis-希尔曼（MBH）的一个分子乙酸盐annulations 1与2-（亚苄基）二氢化茚-1,3-二酮的两个分子2或methyleneindolinones 4已根据非常发达在中等至极好的收率和良好的非对映选择性下，温和的条件分别产生多立体异构的双螺环己烷3和5。这种胺催化的环化反应是构建双螺环己烷基序的一种新颖而有效的方法，并且就相应的膦催化的[3 + 2]环化反应而言，也展示了胺和膦之间的发散催化作用。
• Enantioselective Michael Reaction of Cyclic β-Ketoesters with Morita–Baylis–Hillman Derivatives Using a Phase-Transfer Catalyst
  作者：Ryukichi Takagi、Emi Fujii、Hirotoshi Kondo

  DOI：10.1021/acs.joc.8b01777

  日期：2018.9.21

  enantioselective Michael reaction of cyclic β-ketoesters with Morita–Baylis–Hillman (MBH) derivatives using a phase-transfer catalyst. Cyclic β-ketoesters reacted with MBH derivatives to stereoselectively generate a quaternary carbon center in the presence of cinchona alkaloid-derived bulky ammonium catalyst, and aqueous KOH and Michael adducts bearing an acrylate moiety were obtained in good chemical yields

  这项研究的目的是使用相转移催化剂开发一种高β-对映体选择性的环状β-酮酸酯与Morita-Baylis-Hillman（MBH）衍生物的反应。在金鸡纳生物碱衍生的大块铵催化剂存在下，环状β-酮酯与MBH衍生物反应，立体选择性地生成季碳中心，并以良好的化学收率和良好的对映选择性获得了含水的KOH和带有丙烯酸酯部分的Michael加合物。
• Distinct reactivity of Morita–Baylis–Hillman acetates as a novel C2 component in amine-catalyzed [2 + 2 + 2] and [2 + 4] annulations
  作者：Rongshun Chen、Silong Xu、Liyi Wang、Yuhai Tang、Zhengjie He

  DOI：10.1039/c3cc41419a

  日期：——

  Amine-catalyzed [2 + 2 + 2] and [2 + 4] annulations of Morita–Baylis–Hillman (MBH) acetates with cyano activated alkenes and 1,3-azadienes have been developed to provide cyclohexanes and tetrahydropyridines. In the annulations, MBH acetates serve as a novel C2 component with an inactive homoallylic methyl involved in the bond formation.

  在胺催化下，莫里塔-贝利斯-希尔曼（MBH）醋酸盐与氰基活化烯类和 1,3-氮杂二烯发生了[2 + 2 + 2]和[2 + 4]环化反应，生成了环己烷和四氢吡啶。在环化反应中，MBH 乙酸酯作为一种新的 C2 组分，其不活泼的均烯丙基甲基参与了键的形成。
• Amine-Catalyzed Tandem Reactions of Morita-Baylis-Hillman Acetates with Isatins: Facile Synthesis of 3-Hydroxyoxindoles
  作者：Rongshun Chen、Xia Fan、Zhaozhong Xu、Zhengjie He

  DOI：10.1002/ejoc.201701274

  日期：2017.11.9

  amine-catalyzed reaction between Morita–Baylis–Hillman (MBH) acetates and isatins to provide facile access to structurally interesting 3-hydroxyoxindoles in moderate to good yields with diastereomeric ratios of 1:1 has been developed. A wide variety of isatin derivatives were tolerated under the conditions of this tandem reaction. Notably, the inert homoallylic methyl group of MBH acetate 1 was directly

  Morita-Baylis-Hillman (MBH) 醋酸盐和靛红之间的胺催化反应已经开发出来，可以轻松获得结构有趣的 3-羟基吲哚，收率中等至良好，非对映体比例为 1:1。在这种串联反应的条件下，可以耐受多种靛红衍生物。值得注意的是，MBH 醋酸酯 1 的惰性同烯丙基甲基直接参与了键形成步骤，随后在温和条件下进行 [4+2] 环化，得到所需的产物。