3-hydroxy-2-methylene-pentanoic acid methyl ester | 18052-21-6

• 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: 3-hydroxy-2-methylene-pentanoic acid methyl ester
• 英文别名: methyl 3-hydroxy-2-methylenepentanoate；methyl 2-(1-hydroxypropyl)acrylate；Methyl 3-hydroxy-2-methylidenepentanoate
• CAS: 18052-21-6
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: WXZUVXFBEAOGOZ-UHFFFAOYSA-N

物化性质

• 沸点：
  55-56 °C(Press: 2 Torr)
• 密度：
  1.027±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  3-hydroxy-2-methylene-pentanoic acid methyl ester 在 N-溴代丁二酰亚胺(NBS) 、 二甲基硫 作用下， 生成 metyl 2-(bromomethyl)-2-pentenoate
  参考文献：
  名称：

  Kinetic resolution in the directed hydrogenation of N-substituted -(aminoalkyl) acrylates, precursors of optically active -amino acids.

  摘要：

  DOI：

  10.1016/s0040-4039(00)96075-1
• 作为产物：
  描述：

  methyl 3-((tert-butoxycarbonyl)oxy)-2-methylenepentanoate 在 三乙烯二胺 、 水 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以60%的产率得到3-hydroxy-2-methylene-pentanoic acid methyl ester
  参考文献：
  名称：

  Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water

  摘要：

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.

  DOI：

  10.1021/jo201096e

文献信息

• Correlation between p<i>K</i>_a and Reactivity of Quinuclidine-Based Catalysts in the Baylis−Hillman Reaction:  Discovery of Quinuclidine as Optimum Catalyst Leading to Substantial Enhancement of Scope
  作者：Varinder K. Aggarwal、Ingo Emme、Sarah Y. Fulford

  DOI：10.1021/jo026671s

  日期：2003.2.1

  powerful combination of quinuclidine with methanol was tested with a host of aldehydes and Michael acceptors. Not only were the reactions more efficient and faster than previously reported, but now new substrates that were previously unreactive could be employed. Notable examples include the use of acetylenic aldehydes and the employment of vinyl sulfones, acrylamides, delta-lactones, and even alpha

  在Baylis-Hillman反应中，已研究了多种基于奎尼丁的催化剂的反应性，并且毫无例外地已确定了碱的碱性和反应性之间的直接相关性。用括号中给出的共轭酸的pK（a）（在水中测量）建立了以下反应顺序：奎尼丁（11.3），3-羟基奎尼丁（9.9），DABCO（8.7），3-乙酰氧基奎尼丁（9.3） ，3-氯喹核苷（8.9）和奎宁环酮（7.2）。通过比较DABCO和3-乙酰氧基奎宁在DMSO中的相对碱性，分析了基于pK（a）的DABCO高于预期的反应性。发现在非质子溶剂中，DABCO的碱性比3-乙酰氧基喹核苷高0.6 pK（a）单位，因此在胺的pK（a）及其反应性之间建立了直接联系。与先前报道相反的文献工作相反，发现具有最高pK（a）的奎尼丁是最活泼的催化剂。与奎尼丁的反应曲线显示出显着的自催化作用，这表明质子供体的存在可能进一步提高速率。因此，研究了一系列带有极性XH键的添加剂，发现甲醇，三
• Regioselective S_N2' Mitsunobu reaction of Morita–Baylis–Hillman alcohols: A facile and stereoselective synthesis of α-alkylidene-β-hydrazino acid derivatives
  作者：Silong Xu、Jian Shang、Junjie Zhang、Yuhai Tang

  DOI：10.3762/bjoc.10.98

  日期：——

  regioselective SN2' Mitsunobu reaction between Morita-Baylis-Hillman (MBH) alcohols, azodicarboxylates, and triphenylphosphine is developed, which provides an easy access to alpha-alkylidene-beta-hydrazino acid derivatives in high yields and good stereoselectivity. This reaction represents the first direct transformation of MBH alcohols into hydrazines.

  开发了 Morita-Baylis-Hillman (MBH) 醇、偶氮二羧酸盐和三苯基膦之间的高度区域选择性 SN2' Mitsunobu 反应，可轻松获得高产率和良好立体选择性的 α-亚烷基-β-肼酸衍生物。该反应代表了 MBH 醇首次直接转化为肼。
• Development of catalysts for the Baylis–Hillman reaction: the application of tetramethylguanidine and attempts to use a supported analogue
  作者：Nicholas E. Leadbeater、Cornelia van der Pol

  DOI：10.1039/b106267k

  日期：2001.11.1

  We show here that tetramethylguanidine (TMG) is a useful catalyst for the Baylis–Hillman reaction of aldehydes with methyl acrylate, showing good activity with a range of aldehyde substrates and, unlike many other catalysts or catalyst mixtures, it can be used to good effect with simple aliphatic aldehydes. We show that the activity of the catalyst is decreased when the reaction is run using solvents rather than solvent-free but, in the case where a solvent is necessary, dichloromethane offers the best results. Attempts to use supported or derivatised TMG complexes as catalysts for the reaction have been unsuccessful suggesting that the presence of an amine hydrogen is key to the activity of TMG. Attempts to use stabilised aliphatic phosphines as catalysts for the reaction have proven partly successful, with only modest yields of product being obtained with 2-(dicyclohexylphosphino)biphenyl and 2-(di-tert-butylphosphino)biphenyl. The Verkade superbase, P(MeNCH2CH2)3N, proved inactive as a catalyst, an adduct with the acrylate being the only product formed.

  本文研究表明，四甲基胍（TMG）是巴利斯-希尔曼反应中醛与甲基丙烯酸酯的有效催化剂，对一系列醛底物显示出良好的活性，并且与其他许多催化剂或催化剂混合物不同，它可有效地用于简单脂肪醛。研究表明，当反应在有机溶剂中进行而非无溶剂时，催化剂的活性会降低，但在需要溶剂的情况下，二氯甲烷能提供最佳结果。试图使用负载或衍生化的TMG配合物作为该反应的催化剂均未成功，这表明胺氢的存在对TMG的活性至关重要。尝试使用稳定化的脂肪族膦作为催化剂取得了部分成功，仅在使用2-(二环己基膦基)联苯和2-(二叔丁基膦基)联苯时获得了适度的产物收率。Verkade超碱，即P(MeNCH2CH2)3N，作为催化剂无效，仅形成与丙烯酸酯的加合物。
• Superior amine catalysts for the Baylis–Hillman reaction: the use of DBU and its implications†
  作者：Varinder K. Aggarwal、Andrea Mereu

  DOI：10.1039/a907754e

  日期：——

  DBU, which is normally regarded as a hindered and non-nucleophilic base, is in fact the optimum catalyst for the Baylis–Hillman reaction, providing adducts at much faster rates than using DABCO or 3HQD; the scope of the Baylis–Hillman reaction is enhanced using this catalyst and implications of this finding are discussed.

  DBU通常被认为是一种位阻大且非亲核性的碱，但实际上它是Baylis-Hillman反应的最佳催化剂，能够比使用DABCO或3HQD更快速地提供加合物；使用这种催化剂可以扩大Baylis-Hillman反应的应用范围，并且讨论了这一发现的含义。
• One-Pot Preparation of 1-Acyl-1-methoxycarbonyloxiranes and 1-Acyl-1-cyanooxiranes from Methyl 3-Hydroxy-2-methylenealkanoates or 3-Aryl-3-hydroxy-2-methylenepropanenitriles
  作者：André Foucaud、Eliane le Rouillé

  DOI：10.1055/s-1990-27016

  日期：——

  The reaction of sodium hypochlorite with methyl 3-hydroxy-2methylenealkanoates or 3-aryl-3-hydroxy-2-methylenepropanenitriles, dispersed on silica gel, in acetonitrile leads to oxidation of the alcohol function and epoxidation of the methylene group to give 2,2-disubstituted oxiranes in good yield.

  次氯酸钠与甲基3-羟基-2-亚甲基烷酸酯或3-芳基-3-羟基-2-亚甲基丙腈在硅胶上分散，并在乙腈中反应，导致醇功能被氧化，亚甲基被环氧化，从而以良好产率得到2,2-二取代的环氧乙烷。