dimethyl (E)-2-methyl-3-((E)-3-((4S)-2-oxido-1,3,2-dioxathiolan-4-yl)allylidene)succinate | 1579962-35-8

• 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: dimethyl (E)-2-methyl-3-((E)-3-((4S)-2-oxido-1,3,2-dioxathiolan-4-yl)allylidene)succinate
• CAS: 1579962-35-8
• 化学式: C₁₂H₁₆O₇S
• 分子量: 304.321
• InChiKey: ASGHMQUWGSDTQZ-LLAVVKBUSA-N

反应信息

• 作为反应物：
  描述：

  dimethyl (E)-2-methyl-3-((E)-3-((4S)-2-oxido-1,3,2-dioxathiolan-4-yl)allylidene)succinate 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以73%的产率得到dimethyl (E)-2-methyl-3-((E)-4-oxopent-2-en-1-ylidene)succinate
  参考文献：
  名称：

  Base-Stimulated 1,2-, 1,4-, and 1,6-Eliminations in Suitably Substituted Alkylidenesuccinates Leading to Natural and Unnatural Conjugated Alkenyl(methyl)maleic Anhydrides

  摘要：

  With dimethyl maleate as the starting material, facile stereoselective syntheses of natural and unnatural conjugated alkenyl(methyl)maleic anhydrides have been described. The key reactions were base-endorsed novel 1,2-, 1,4-, and 1,6-eliminations in the corresponding alkylidenesuccinate derivatives. The 1,2-eliminations in cyclic carbonate and sulfite by regioselective abstraction of methine protons with the respective release of CO2 and SO2 provided a conjugated ketone product. The characteristic 1,4- and 1,6-elimination reactions with respective release of acetone and mesylate furnished the corresponding unsaturated alcohols. The obtained allylic alcohols were transformed into conjugated alkenyl(methyl)maleic anhydrides via oxidation followed by a Horner-Wadsworth-Emmons reaction pathway in very good yields. The mechanistic aspects involved in these significant elimination reactions have also been described in brief.

  DOI：

  10.1021/jo402857r
• 作为产物：
  描述：

  dimethyl (E)-2-((S,E)-4,5-dihydroxypent-2-en-1-ylidene)-3-methylsuccinate 在 氯化亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以83%的产率得到dimethyl (E)-2-methyl-3-((E)-3-((4S)-2-oxido-1,3,2-dioxathiolan-4-yl)allylidene)succinate
  参考文献：
  名称：

  Base-Stimulated 1,2-, 1,4-, and 1,6-Eliminations in Suitably Substituted Alkylidenesuccinates Leading to Natural and Unnatural Conjugated Alkenyl(methyl)maleic Anhydrides

  摘要：

  With dimethyl maleate as the starting material, facile stereoselective syntheses of natural and unnatural conjugated alkenyl(methyl)maleic anhydrides have been described. The key reactions were base-endorsed novel 1,2-, 1,4-, and 1,6-eliminations in the corresponding alkylidenesuccinate derivatives. The 1,2-eliminations in cyclic carbonate and sulfite by regioselective abstraction of methine protons with the respective release of CO2 and SO2 provided a conjugated ketone product. The characteristic 1,4- and 1,6-elimination reactions with respective release of acetone and mesylate furnished the corresponding unsaturated alcohols. The obtained allylic alcohols were transformed into conjugated alkenyl(methyl)maleic anhydrides via oxidation followed by a Horner-Wadsworth-Emmons reaction pathway in very good yields. The mechanistic aspects involved in these significant elimination reactions have also been described in brief.

  DOI：

  10.1021/jo402857r