methyl (3R)-3-hydroxy-2-methylene-5-phenylpentanoate

• 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 (3R)-3-hydroxy-2-methylene-5-phenylpentanoate
• 英文别名: (R)-methyl 3-hydroxy-2-methylene-5-phenylpentanoate；methyl (R)-3-hydroxy-2-methylene-5-phenylpentanoate；methyl (3R)-3-hydroxy-2-methylidene-5-phenylpentanoate
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: UAMOPHYQNOARPA-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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 (3R)-3-hydroxy-2-methylene-5-phenylpentanoate 在 叔丁基过氧化氢 、 甲基锂 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 以54%的产率得到
  参考文献：
  名称：

  Study of the stereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters

  摘要：

  The diastereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters has been studied. The 3-hydroxy-2-methylene esters were obtained through a Morita-Baylis-Hillman reaction. The resulting epoxyesters were treated with thiophenol for transformation into 2,3-dihydroxy-2-((phenylthio)methyl), which upon treatment with triphosgene afforded the corresponding cyclic carbonates. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.11.014
• 作为产物：
  描述：

  苯丙醛 、 丙烯酸甲酯（MA） 在 三乙烯二胺 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 48.0h， 以99%的产率得到methyl (3R)-3-hydroxy-2-methylene-5-phenylpentanoate
  参考文献：
  名称：

  Study of the stereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters

  摘要：

  The diastereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters has been studied. The 3-hydroxy-2-methylene esters were obtained through a Morita-Baylis-Hillman reaction. The resulting epoxyesters were treated with thiophenol for transformation into 2,3-dihydroxy-2-((phenylthio)methyl), which upon treatment with triphosgene afforded the corresponding cyclic carbonates. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.11.014

文献信息

• β-Isocupreidine–hexafluoroisopropyl acrylate method for asymmetric Baylis–Hillman reactions
  作者：Ayako Nakano、Sakie Kawahara、Saori Akamatsu、Kenji Morokuma、Mari Nakatani、Yoshiharu Iwabuchi、Keisuke Takahashi、Jun Ishihara、Susumi Hatakeyama

  DOI：10.1016/j.tet.2005.09.072

  日期：2006.1

  Key features of the β-isocupreidine (β-ICD)-catalyzed asymmetric Baylis–Hillman reaction of aldehydes with 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) are presented. In addition, an improved method using azeotropically dried β-ICD is described.

  介绍了β-异iso啶（β-ICD）催化醛与1,1,1,3,3,3-六氟丙烯酸异丙酯（HFIPA）的不对称Baylis-Hillman反应的关键特征。另外，描述了使用共沸干燥的β-ICD的改进方法。
• α-Isocupreine, an Enantiocomplementary Catalyst of β-Isocupreidine
  作者：Yoshito Nakamoto、Fumiya Urabe、Keisuke Takahashi、Jun Ishihara、Susumi Hatakeyama

  DOI：10.1002/chem.201302665

  日期：2013.9.16

  Complementary chemistry! α‐Isocupreine (α‐ICPN) was synthesized for the first time in one step from quinine by treatment with CF3SO3H (see scheme). This compound serves as an enantiocomplementary catalyst to β‐isocupreidine (β‐ICD) in the Morita–Baylis–Hillman reaction.

  互补化学！通过CF 3 SO 3 H处理，从奎宁一步一步合成了α-异cupreine（α-ICPN）（参见方案）。在Morita-Baylis-Hillman反应中，该化合物可作为β-异cupreidine（β-ICD）的对映体互补催化剂。
• Enantioselective Synthesis of the Optically Active α-Methylene-β-hydroxy Esters, Equivalent Compounds to Morita−Baylis−Hillman Adducts, Using Successive Asymmetric Aldol Reaction and Oxidative Deselenization
  作者：Isamu Shiina、Yu-suke Yamai、Takahisa Shimazaki

  DOI：10.1021/jo051276y

  日期：2005.9.1

  The asymmetric aldol reaction of a tetra-substituted ketene silyl acetal including an alkylseleno group with aldehydes has been developed by the promotion of Sn(OTf)2 coordinated with a chiral diamine to afford the corresponding aldols having chiral quaternary centers at the α-positions. The facile oxidative deselenization of these aldol compounds produces optically active α-methylene-β-hydroxy esters

  通过促进与手性二胺配位的Sn（OTf）2得到相应的具有在α-位的手性季中心的醛醇，已经开发了包括烷基硒烯基的四取代的乙烯酮甲硅烷基乙缩醛与醛的不对称醛醇缩合反应。这些羟醛化合物的轻度氧化脱硒作用产生旋光性α-亚甲基-β-羟基酯，它们对应于由不对称Morita-Baylis-Hillman反应制备的加合物。
• Kinetic Resolution of α-Methylene-<i>β-</i>hydroxy Esters Catalyzed by Acyl Transfer Catalyst <i>An</i>-PIQ
  作者：Shan-Shan Jiang、Qin-Chang Xu、Ming-Yu Zhu、Xingxin Yu、Wei-Ping Deng

  DOI：10.1021/acs.joc.5b00073

  日期：2015.3.20

  A highly efficient nonenzymatic kinetic resolution of a series of structurally diverse racemic alpha-methylene-beta-hydroxy esters utilizing the acyl transfer catalyst An-PIQ and propionic anhydride is reported. This procedure provides recovered alcohols with extremely high ees (up to >99%) in reasonable conversions and excellent selectivity factors (S up to 108). Several synthetically important substrates were resolved in gram-scale reactions, and highly optically pure alpha-methylene-beta-hydroxy esters were obtained with excellent S values and good yields.
• Study of the stereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters
  作者：Antonio Latorre、José A. Sáez、Santiago Rodríguez、Florenci V. González

  DOI：10.1016/j.tet.2013.11.014

  日期：2014.1

  The diastereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters has been studied. The 3-hydroxy-2-methylene esters were obtained through a Morita-Baylis-Hillman reaction. The resulting epoxyesters were treated with thiophenol for transformation into 2,3-dihydroxy-2-((phenylthio)methyl), which upon treatment with triphosgene afforded the corresponding cyclic carbonates. (C) 2013 Elsevier Ltd. All rights reserved.