dimethyl 2-allyl-2-(4-oxobutyl)malonate | 1181217-78-6

• 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 2-allyl-2-(4-oxobutyl)malonate
• 英文别名: Dimethyl 2-(4-oxobutyl)-2-prop-2-enylpropanedioate
• CAS: 1181217-78-6
• 化学式: C₁₂H₁₈O₅
• 分子量: 242.272
• InChiKey: IKNMXKFKAIEVNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-allyl-2-(4-oxobutyl)malonate 、 tert-butyldimethylsilyl ester of aci-1-nitropropane 在 ammonium cerium (IV) nitrate 、 5-benzyl-2-t-butyl-3-methyl-4-oxoimidazolidinium trifluoroacetate 、 水 、 sodium 2,2,2-trifluoroacetate 、 sodium tetrahydroborate 作用下， 以 丙酮 、 乙醚 、 乙醇 为溶剂， 反应 18.0h， 生成 dimethyl 2-allyl-2-[3-(hydroxymethyl)-4-nitrohexyl]malonate 、 dimethyl 2-allyl-2-[3-(hydroxymethyl)-4-nitrohexyl]malonate
  参考文献：
  名称：

  Enantioselective Aldehyde α-Nitroalkylation via Oxidative Organocatalysis

  摘要：

  The first enantioselective organocatalytic alpha-nitroatkylation of aldehydes has been accomplished. The aforementioned process involves the oxidative coupling of an enamine intermediate, generated transiently via condensation of an amine catalyst with an aldehyde, with a silyl. nitronate to produce a beta-nitroaldehyde. Two methods, one that furnishes the syn beta-nitroaldehyde and a second that provides access to the anti isomer, have been developed. Data are presented to support a hypothesis that explains this phenomenon in terms of a silyl group-controlled change in mechanism. Finally, a three-step procedure for the synthesis of both syn- and anti-alpha,beta-disubstituted beta-amino acids is presented.

  DOI：

  10.1021/ja904504j
• 作为产物：
  描述：

  在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 20.0h， 以2.1 g的产率得到dimethyl 2-allyl-2-(4-oxobutyl)malonate
  参考文献：
  名称：

  Enantioselective Aldehyde α-Nitroalkylation via Oxidative Organocatalysis

  摘要：

  The first enantioselective organocatalytic alpha-nitroatkylation of aldehydes has been accomplished. The aforementioned process involves the oxidative coupling of an enamine intermediate, generated transiently via condensation of an amine catalyst with an aldehyde, with a silyl. nitronate to produce a beta-nitroaldehyde. Two methods, one that furnishes the syn beta-nitroaldehyde and a second that provides access to the anti isomer, have been developed. Data are presented to support a hypothesis that explains this phenomenon in terms of a silyl group-controlled change in mechanism. Finally, a three-step procedure for the synthesis of both syn- and anti-alpha,beta-disubstituted beta-amino acids is presented.

  DOI：

  10.1021/ja904504j

文献信息

• Enantioselective Aldehyde α-Nitroalkylation via Oxidative Organocatalysis
  作者：Jonathan E. Wilson、Anthony D. Casarez、David W. C. MacMillan

  DOI：10.1021/ja904504j

  日期：2009.8.19

  The first enantioselective organocatalytic alpha-nitroatkylation of aldehydes has been accomplished. The aforementioned process involves the oxidative coupling of an enamine intermediate, generated transiently via condensation of an amine catalyst with an aldehyde, with a silyl. nitronate to produce a beta-nitroaldehyde. Two methods, one that furnishes the syn beta-nitroaldehyde and a second that provides access to the anti isomer, have been developed. Data are presented to support a hypothesis that explains this phenomenon in terms of a silyl group-controlled change in mechanism. Finally, a three-step procedure for the synthesis of both syn- and anti-alpha,beta-disubstituted beta-amino acids is presented.