methyl (Z)-6-acetoxy-2-(methoxycarbonyl)-2-(but-2'-ynyl)-hex-4-enoate | 844821-22-3

• 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)-6-acetoxy-2-(methoxycarbonyl)-2-(but-2'-ynyl)-hex-4-enoate
• 英文别名: methyl (Z)-6-acetoxy-2-(methoxycarbonyl)-2-(but-2-ynyl)-hex-4-enoate；dimethyl 2-(but-2-ynyl)-2-((Z)-4-acetoxybut-2-enyl)malonate；dimethyl 2-[(Z)-4-acetyloxybut-2-enyl]-2-but-2-ynylpropanedioate
• CAS: 844821-22-3
• 化学式: C₁₅H₂₀O₆
• 分子量: 296.32
• InChiKey: BNEBXKUHLSXXOT-FPLPWBNLSA-N

物化性质

• 沸点：
  375.3±42.0 °C(Predicted)
• 密度：
  1.124±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (Z)-6-acetoxy-2-(methoxycarbonyl)-2-(but-2'-ynyl)-hex-4-enoate 在 2,2'-联吡啶 、 palladium diacetate 、 溶剂黄146 作用下， 反应 48.0h， 以87%的产率得到dimethyl 3-(1-acetoxy-ethylidene)-4-vinyl-cyclopentane-1,1-dicarboxylate
  参考文献：
  名称：

  Cycloisomerization of 1,6-Enynes Using Acetate as a Nucleophile under Palladium(II) Catalysis

  摘要：

  An efficient method for the synthesis of five-membered carbo- and heterocyclic compounds, including fused rings, was reported using acetate as a nucleophile in the cyclization of 1,6-enynes under palladium(II) catalysis. The reaction is initiated by trans-acetoxypalladation of the alkynes and quenched by either trans- or cis-deacetoxypalladation in the presence of 2,2'-bipyridine as the ligand. An example of the catalytic asymmetric cyclization is presented with moderate enantioselectivity using chiral bisoxazoline ligand.

  DOI：

  10.1021/jo048414o
• 作为产物：
  描述：

  丙二酸二甲酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.33h， 生成 methyl (Z)-6-acetoxy-2-(methoxycarbonyl)-2-(but-2'-ynyl)-hex-4-enoate
  参考文献：
  名称：

  Cycloisomerization of 1,6-Enynes Using Acetate as a Nucleophile under Palladium(II) Catalysis

  摘要：

  An efficient method for the synthesis of five-membered carbo- and heterocyclic compounds, including fused rings, was reported using acetate as a nucleophile in the cyclization of 1,6-enynes under palladium(II) catalysis. The reaction is initiated by trans-acetoxypalladation of the alkynes and quenched by either trans- or cis-deacetoxypalladation in the presence of 2,2'-bipyridine as the ligand. An example of the catalytic asymmetric cyclization is presented with moderate enantioselectivity using chiral bisoxazoline ligand.

  DOI：

  10.1021/jo048414o

文献信息

• The use of iminopyridines as efficient ligands in the palladium(II)-catalyzed cyclization of (Z)-4′-acetoxy-2′-butenyl 2-alkynoates
  作者：Juan Song、Qi Shen、Fan Xu、Xiyan Lu

  DOI：10.1016/j.tet.2007.04.006

  日期：2007.6

  Iminopyridines were found to be a sort of efficient bidentate ligands for the palladium(II)-catalyzed cyclization of (Z)-4′-acetoxy-2′-butenyl 2-alkynoates in acetic acid to afford the α-(Z)-acetoxyalkylidene-β-vinyl-γ-butyrolactones. The iminopyridine ligands could not only inhibit β-hydride elimination but also stabilize the vinyl-palladium intermediate in acetic acid in the reaction.

  发现氨基吡啶是一种有效的二齿配体，可用于钯（II）催化乙酸中的（Z）-4'-乙酰氧基-2'-丁烯基2-炔酸酯的环化反应，得到α-（Z）-乙酰氧基亚烷基-β-乙烯基-γ-丁内酯。亚氨基吡啶配体不仅可以抑制β-氢化物的消除，而且可以稳定反应中乙酸中的乙烯基-钯中间体。
• Cationic Pd(II)-catalyzed arylative cyclization of 1,6-enynes with arylboronic acids
  作者：Kun Shen、Xiuling Han、Xiyan Lu、Zhiyong Hu

  DOI：10.1016/j.tetlet.2017.08.036

  日期：2017.9

  A cationic Pd(II)-catalyzed redox neutral arylative cyclization of enynes by using beta-acetoxy elimination as the quenching step has been developed. The reaction offers an efficient method to access a variety of carbocycles and N-heterocycles bearing an exocyclic double bond. (C) 2017 Elsevier Ltd. All rights reserved.
• Rhodium-Catalyzed Cyclization of 1,6-Enynes Triggered by Addition of Arylboronic Acids
  作者：Tomoya Miura、Masahiko Shimada、Masahiro Murakami

  DOI：10.1021/ja0435079

  日期：2005.2.1

  1,6-Enynes reacted with arylboronic acids in the presence of a catalytic amount of a rhodium(I) complex under mild conditions to give (Z)-1-(1-arylethylidene)-2-vinylcyclopentanes. The regioselective addition of an arylrhodium(I) species across the carbon-carbon triple bond triggered the cyclization process. Intramolecular carborhodation onto the pendent alkene in a 5-exo mode furnished a five-membered ring. Finally, the rhodium(I) methoxide generated by beta-methoxy elimination reacted with the arylboronic acid to promote the next catalytic cycle.