methyl (Z)-4-hydroxy-3-iodobut-2-enoate | 1246264-05-0

• 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 (Z)-4-hydroxy-3-iodobut-2-enoate
• 英文别名: (Z)-methyl 3-iodo-4-hydroxybutenoate
• CAS: 1246264-05-0
• 化学式: C₅H₇IO₃
• 分子量: 242.013
• InChiKey: DVWWEQPDIQZQPT-RQOWECAXSA-N

物化性质

• 沸点：
  276.3±40.0 °C(Predicted)
• 密度：
  1.946±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.47
• 重原子数：
  9.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl (Z)-4-hydroxy-3-iodobut-2-enoate 、 (E)-1-[3-hydroxy-2-(tributylstannyl)prop-1-en-1-yl]cyclohexan-1-ol 在 钯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以66%的产率得到
  参考文献：
  名称：

  Fully Substituted Pyranones via Quasi-Heterogeneous Genuinely Ligand-Free Migita–Stille Coupling of Iodoacrylates

  摘要：

  Migita-Stille coupling of (Z)-β-iodoacrylates with (E)-α-stannyl allylic alcohols to furnish 5-alkylidene-4-substituted-5,6-dihydro-2H-pyran-2-ones is efficiently catalyzed by 2% Pd black in DMF, while Pd(PPh3)4 is inactive. Heterogeneous Pd released in solution is most likely responsible for the catalysis. The reaction is applicable to other substrates, without having to resort to ligands, additives, and/or solid support for Pd. The resulting pyranones can be rearranged to fully functionalized pyranones in another single step.

  DOI：

  10.1021/ol5035113
• 作为产物：
  描述：

  4-羟基-2-丁酸甲酯 在 lithium iodide trihydrate 、 溶剂黄146 作用下， 以 乙腈 为溶剂， 以54%的产率得到methyl (Z)-4-hydroxy-3-iodobut-2-enoate
  参考文献：
  名称：

  Synthesis of demethylated nidulol via an intramolecular Michael reaction

  摘要：

  An expeditious synthesis of 5,7-dihydroxy-6-methylphthalide from open-chain precursors is described. The key intermediates, synthons 3 and 4, were readily obtained from accessible materials and were further transformed to a common precursor, a five-membered lactone derivative, via an intramolecular Michael addition. Lactone 2 was aromatised to the phthalide system under basic conditions. The process thus constitutes a formal synthesis of the phthalide framework.

  DOI：

  10.1080/14786410903458265

文献信息

• A New Insight into the Stereoelectronic Control of the Pd ⁰ ‐Catalyzed Allylic Substitution: Application for the Synthesis of Multisubstituted Pyran‐2‐ones via an Unusual 1,3‐Transposition
  作者：Zbyněk Brůža、Jiří Kratochvíl、Jeremy N. Harvey、Lubomír Rulíšek、Lucie Nováková、Jana Maříková、Jiří Kuneš、Pavel Kočovský、Milan Pour

  DOI：10.1002/chem.201900323

  日期：2019.6.18

  Pyran‐2‐ones 3 undergo a novel Pd0‐catalyzed 1,3‐rearrangement to afford isomers 6. The reaction proceeds via an η2‐Pd complex, the pyramidalization of which (confirmed by quantum chemistry calculations) offers a favorable antiperiplanar alignment of the Pd−C and allylic C−O bonds (C), thus allowing the formation of an η3‐Pd intermediate. Subsequent rotation and rate‐limiting recombination with the

  Pyran-2-ones 3经过新的Pd 0催化的1,3-重排，得到异构体6。经由η该反应进行2 -Pd复杂，pyramidalization其中（由量子化学计算确认）提供的Pd-C和烯丙基C-O键（的有利antiperiplanar对准Ç），从而允许一个η的形成3 -Pd中间体。随后的旋转和与羧酸酯臂的限速重组产生异构体吡喃-2-酮6。计算出的自由能半定量地再现了观察到的动力学。