2-[(E)-3-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-allyl]-2-prop-2-ynyl-malonic acid dimethyl ester | 95124-01-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-[(E)-3-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-allyl]-2-prop-2-ynyl-malonic acid dimethyl ester
• 英文别名: dimethyl 2-[(E)-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enyl]-2-prop-2-ynylpropanedioate
• CAS: 95124-01-9
• 化学式: C₁₆H₂₂O₆
• 分子量: 310.347
• InChiKey: SJHIKDIPQKRWLM-GUOLPTJISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-[(E)-3-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-allyl]-2-prop-2-ynyl-malonic acid dimethyl ester 在 二乙酰二(三苯基膦)钯 、 三苯基膦 作用下， 以 氘代苯 为溶剂， 反应 1.75h， 以71%的产率得到3-[1-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-meth-(E)-ylidene]-4-methylene-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.

  DOI：

  10.1021/ja00089a015
• 作为产物：
  描述：

  炔丙基丙二酸二甲酯 、 (4R,3RS)-1-(2,2-dimethyl-[1,3]dioxolan-4-yl)allyl acetate 在 苯磺酰胺 、 四(三苯基膦)钯 、 sodium hydride 、 三苯基膦 作用下， 生成 2-[(E)-3-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-allyl]-2-prop-2-ynyl-malonic acid dimethyl ester
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.

  DOI：

  10.1021/ja00089a015

文献信息

• Cyclization via isomerization: a palladium(2+)-catalyzed carbocyclization of 1,6-enynes to 1,3- and 1,4-dienes
  作者：Barry M. Trost、Mark Lautens

  DOI：10.1021/ja00292a065

  日期：1985.3