ethyl (2R,3R)-2-methyl-5-oxo-2-prop-2-enyloxolane-3-carboxylate | 90832-98-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: ethyl (2R,3R)-2-methyl-5-oxo-2-prop-2-enyloxolane-3-carboxylate
• CAS: 90832-98-7；90833-02-6；90833-06-0
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: BYIJQCJAIFVWIT-GZMMTYOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (2R,3R)-2-methyl-5-oxo-2-prop-2-enyloxolane-3-carboxylate 、 sodium hydroxide 生成 2-Methyl-5-oxo-2-prop-2-enyloxolane-3-carboxylic acid
  参考文献：
  名称：

  GAUDEMAR-BARDONE, F.;MLADENOVA, M.;COUFFIGNAL, R., SYNTHESIS, BRD, 1985, N 11, 1043-1047

  摘要：

  DOI：
• 作为产物：
  描述：

  乙酰琥珀酸二乙酯 、 3-溴丙烯 在 硫酸 、 氯化铵 、 锌 作用下， 生成 ethyl (2R,3R)-2-methyl-5-oxo-2-prop-2-enyloxolane-3-carboxylate 、 (2S,3R)-2-Allyl-2-methyl-5-oxo-tetrahydro-furan-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Stereochemistry and Mechanism of the Chemoselective Allylation of alpha-Substituted beta-Keto Esters with Allyl Bromide Mediated by Zn in NH4Cl(aq)-THF.

  摘要：

  alpha-substituted beta-keto esters were chemoselectively allylated at the keto group by a Zn-mediated reaction with allyl bromide in NH4Cl(aq)-THF. The reactions gave diastereomeric homoallylic alcohols with d.e.s ranging from 28 to 74%. With ethyl 2-chloroacetoacetate, substitution of the chlorine atom by the allyl group took place. Similarly, on allylation of diethyl benzoylmalonate, diethyl malonate was eliminated. These reactions support a radical mechanism. The relative configurations of the formed diastereomers were determined by a combination of H-1 NMR spectroscopy and molecular modeling. The stereochemistry of the diastereomers supports a mechanism including strong association of the keto ester with the metal surface.

  DOI：

  10.3891/acta.chem.scand.51-0785

文献信息

• Synthesis of 3-Ethoxycarbonyl-3-buten-4-olides and 3-Ethoxycarbonyl-4-butanolides
  作者：Françoise Gaudemar-Bardone、Margarita Mladenova、RENÉ Couffignal

  DOI：10.1055/s-1985-31423

  日期：——

  This paper describes a synthesis of 3-acyl-2-alkyl-3-ethoxycarbonylpropanoic acids from ethyl 2-oxoalkanoates and 2-bromoalkanoic acids. These acids are cyclised via intramolecular dehydration to give 2,4-dialkyl-3-ethoxycarbonyl-3-buten-4-olides or are condensed with allylzinc reagents to give the 4-alkenyl-2,4-dialkyl-3-ethoxycarbonyl-4-butanolides.

  本文描述了从乙基2-氧羧酸酯和2-溴烷酸合成3-酰基-2-烷基-3-乙氧基碳酰基丙酸。这些酸通过分子内脱水环化，生成2,4-二烷基-3-乙氧基碳酰基-3-丁烯-4-内酯，或者与烯丙基锌试剂缩合，生成4-烯基-2,4-二烷基-3-乙氧基碳酰基-4-内酯。
• Synthese de β-ethoxycarbonyl λ-lactones
  作者：F. Gaudemar-Bardone、M. Mladenova、R. Couffignal

  DOI：10.1016/s0040-4039(01)80096-4

  日期：1984.1
• Stereochemistry and Mechanism of the Chemoselective Allylation of alpha-Substituted beta-Keto Esters with Allyl Bromide Mediated by Zn in NH4Cl(aq)-THF.
  作者：Matthias Ahonen、Rainer Sjöholm、Bengt Långström、Markku Ahlgrén、Ward T. Robinson、Bryan R. Wood、Ward T. Robinson、Björn O. Roos、Claire Vallance、Bryan R. Wood

  DOI：10.3891/acta.chem.scand.51-0785

  日期：——

  alpha-substituted beta-keto esters were chemoselectively allylated at the keto group by a Zn-mediated reaction with allyl bromide in NH4Cl(aq)-THF. The reactions gave diastereomeric homoallylic alcohols with d.e.s ranging from 28 to 74%. With ethyl 2-chloroacetoacetate, substitution of the chlorine atom by the allyl group took place. Similarly, on allylation of diethyl benzoylmalonate, diethyl malonate was eliminated. These reactions support a radical mechanism. The relative configurations of the formed diastereomers were determined by a combination of H-1 NMR spectroscopy and molecular modeling. The stereochemistry of the diastereomers supports a mechanism including strong association of the keto ester with the metal surface.
• GAUDEMAR-BARDONE, F.;MLADENOVA, M.;COUFFIGNAL, R., SYNTHESIS, BRD, 1985, N 11, 1043-1047
  作者：GAUDEMAR-BARDONE, F.、MLADENOVA, M.、COUFFIGNAL, R.

  DOI：——

  日期：——