Methyl 2-methylidene-3-[(2-methylpropan-2-yl)oxycarbonyloxy]-5-phenylpentanoate | 1330066-94-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl 2-methylidene-3-[(2-methylpropan-2-yl)oxycarbonyloxy]-5-phenylpentanoate
• 英文别名: methyl 2-methylidene-3-[(2-methylpropan-2-yl)oxycarbonyloxy]-5-phenylpentanoate
• CAS: 1330066-94-8
• 化学式: C₁₈H₂₄O₅
• 分子量: 320.386
• InChiKey: POJBLZKGPBOQLV-UHFFFAOYSA-N

物化性质

• 沸点：
  414.3±45.0 °C(Predicted)
• 密度：
  1.082±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  碳酸甲丙酯 、 Methyl 2-methylidene-3-[(2-methylpropan-2-yl)oxycarbonyloxy]-5-phenylpentanoate 以 乙腈 为溶剂， 反应 8.0h， 以38%的产率得到methyl 2-methylene-5-phenyl-3-(pyridin-2-ylmethyl)pentanoate
  参考文献：
  名称：

  2-烷基吡啶与 Morita-Baylis-Hillman 碳酸酯通过串联亲核取代/氮杂-Cope 重排直接 C(sp3)-H 烯丙基化

  摘要：

  描述了 2-烷基吡啶与 Morita-Baylis-Hillman (MBH) 碳酸酯的无碱和无催化剂的 C(sp 3 )-H 烯丙基烷基化反应。该反应的一个合理机制可能涉及串联 S N 2' 型亲核取代，然后是氮杂-科普重排。在反应中可以容忍 2-烷基吡啶上的各种烷基取代基，以 26-91% 的产率得到烯丙基化产物。所开发的方法为 2-烷基吡啶衍生物的烯丙基官能化提供了一种直接且操作简单的策略。

  DOI：

  10.3762/bjoc.17.167

文献信息

• Organocatalytic One-Pot Synthesis of Highly Substituted Pyridazines from Morita-Baylis-Hillman Carbonates and Diazo Compounds
  作者：Haibin Mao、Aijun Lin、Zhongkai Tang、Hongwen Hu、Chengjian Zhu、Yixiang Cheng

  DOI：10.1002/chem.201304295

  日期：2014.2.24

  A biologically inspired organocatalytic one‐pot synthesis of highly functionalized pyridazines, which are ubiquitous structural units in a number of biologically active compounds, has been developed by starting from readily available diazo compounds and Morita–Baylis–Hillman (MBH) carbonates. Under mild reaction conditions, this synthetic route tolerated significant substrate variation to deliver a

  从容易获得的重氮化合物和Morita-Baylis-Hillman（MBH）碳酸盐开始，已经开发出了一种由生物启发的有机催化一锅合成的高官能化哒嗪，它是许多生物活性化合物中普遍存在的结构单元。在温和的反应条件下，该合成途径可承受显着的底物变化，从而提供广泛的取代产物，包括CF 3取代的哒嗪衍生物。此外，可以通过2,2,2-三氟重氮乙烷方便地完成将三氟甲基引入哒嗪环的操作。
• Planar Chiral Phosphino[2.2]paracyclophanol-Catalyzed Highly Regio- and Stereoselective [3+2] Annulation Reaction of Morita–Baylis–Hillman Carbonates with Dicyanomethylideneoxindoles
  作者：Shinji Kitagaki、Mayuka Tsuji、Hideki Teramoto、Naoko Takenaga、Keisuke Yoshida

  DOI：10.3987/com-19-s(f)3

  日期：——

  yields, and high regio-, diastereo-, and enantioselectivities. INTRODUCTION [2.2]Paracyclophane (PCP) is recognized as a useful planar chiral backbone for ligands used in transition metal catalysts.1 A variety of asymmetric reactions based on catalysts with planar chiral PCP-based ligands, combined with appropriate central chirality, have been reported to date.2 However, there is little information available

  为了证明 [2.2] 对环烷作为手性有机催化剂骨架的实用性，我们检测了平面手性伪邻二芳基膦基 [2.2] 对环芳醇 phosphino-PCP-ol，它在伪邻位取代的 PCP 之间具有间隔芳基-ol 骨架和二芳基膦基。我们在 Morita-Baylis-Hillman 碳酸盐的 [3+2] 环化反应中测试了这种催化剂，该碳酸盐衍生自芳香醛和丙烯酸甲酯，与 3-(二氰基亚甲基)-2-羟吲哚。该催化剂以高产率和高区域、非对映和对映选择性产生所需的 3-螺环戊烯-2-羟吲哚。简介 [2.2] 对环芳烷 (PCP) 被认为是过渡金属催化剂中使用的配体的有用平面手性骨架。1 基于具有平面手性 PCP 配体的催化剂的各种不对称反应，结合适当的中心手性，迄今为止已有报道。 2 然而，关于开发基于 PCP 的有机催化剂的信息很少。 3 在这种情况下，我们开发了膦基-PCP-醇催化剂 (Sp)-1，其在拟邻位取代的
• Highly Regio- and Diastereoselective [3+2]-Annulation Reaction of Morita–Baylis–Hillman Carbonates with Pyrazolones Catalyzed by Tertiary Phosphines
  作者：Zhiwei Miao、Weiping Zheng、Yuming Li、Jiayong Zhang、Siyi Du

  DOI：10.1055/s-0036-1589030

  日期：2017.8

  literature. A phosphine-catalyzed [3+2] annulation between N-phenylpyrazolone derivatives and Morita–Baylis–Hillman carbonates for the synthesis of chiral heterocyclic systems containing spiro[cyclopentane-3,3′-pyrazole] scaffolds has been developed. The reaction afforded the desired products in moderate to high yields (up to 97%) with good to excellent diastereoselectivities (up to 20:1). A plausible reaction

  摘要 已开发了膦催化的N-苯基吡唑啉酮衍生物和Morita-Baylis-Hillman碳酸盐之间的[3 + 2]环状结构，用于合成含有螺环[环戊烷-3,3'-吡唑]骨架的手性杂环系统。该反应以中等至高产率（高达97％）提供了所需产物，具有良好至优异的非对映选择性（高达20∶1）。基于先前的文献，也已经提出了合理的反应机理。 已开发了膦催化的N-苯基吡唑啉酮衍生物和Morita-Baylis-Hillman碳酸盐之间的[3 + 2]环状结构，用于合成含有螺环[环戊烷-3,3'-吡唑]骨架的手性杂环系统。该反应以中等至高产率（高达97％）提供了所需产物，具有良好至优异的非对映选择性（高达20∶1）。基于先前的文献，也已经提出了合理的反应机理。
• Room Temperature Asymmetric Allylic Trifluoromethylation of Morita–Baylis–Hillman Carbonates
  作者：Yun Li、Fang Liang、Qian Li、Yao-chang Xu、Quan-Rui Wang、Lei Jiang

  DOI：10.1021/ol202572u

  日期：2011.11.18

  (DHQD)(2)PHAL-catalyzed asymmetric allylic trifluoromethylation of Morita-Baylis-Hillman adducts using a Rupert-Prakash reagent is reported. This transformation provided the S(N)2' trifluoromethylated products with good yields and excellent enantioselectivities at room temperature. It was also found that the reaction could be accelerated using acetonitrile as cosolvent.

  DHQD催化的Rupert-Prakash试剂催化的Mrita-Baylis-Hillman加成体的不对称 allylic trifluoromethylation反应得以实现。此反应以S(N)2'型三氟etyl甲基化产物为主，产率较高且选择性优异，且可以在常温下高效完成。此外，乙腈作为共溶剂可加速反应进程。
• Asymmetric Organocatalytic Allylic Substitution of Morita–Baylis–Hillman Carbonates with Allylamines for the Synthesis of 2,5-Dihydropyrroles
  作者：Wangsheng Sun、Xiaozhou Ma、Liang Hong、Rui Wang

  DOI：10.1021/jo2011522

  日期：2011.10.7

  The asymmetric allylic substitution reaction of MBH carbonates with allylamines has been developed, which affords N-allyl-beta-amino-alpha-methylene esters in high yields and enantioselectivities. After a subsequent ring-closure metathesis of the products, a series of optically active 2,5-dihydropyrroles could be obtained smoothly in high yields without any loss of enantioselectivity. Finally, a tentative mechanism for rationalization of the reaction has been proposed.