2-[1-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-meth-(Z)-ylidene]-3-oxo-butyric acid methyl ester | 81132-42-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 2-[1-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-meth-(Z)-ylidene]-3-oxo-butyric acid methyl ester
• CAS: 81132-42-5
• 化学式: C₁₁H₁₆O₅
• 分子量: 228.245
• InChiKey: ZKDBQBQLLCIZOG-QMMMGPOBSA-N

物化性质

• 沸点：
  316.9±32.0 °C(Predicted)
• 密度：
  1.170±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.83
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (E)-3-氨基巴豆酸乙酯 、 2-[1-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-meth-(Z)-ylidene]-3-oxo-butyric acid methyl ester 以 乙醇 为溶剂， 反应 4.0h， 以75%的产率得到(S)-4-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,6-dimethyl-1,4-dihydro-pyridine-3,5-dicarboxylic acid 3-ethyl ester 5-methyl ester
  参考文献：
  名称：

  Asymmetric synthesis of 4-alkyl-3,5-dialkoxycarbonyl-2,6-dimethyl-1,4-dihydropyridines

  摘要：

  The first asymmetric synthesis of some novel substituted 1,4-dihydropyridines (1,4-DHPs) is reported. The synthetic methodology used is based on the Michael addition of beta-aminocrotonates to chiral alpha-acetylacrylates, readily available from chiral aldehydes, leading to the 1,4-DHPs in excellent diastereoselectivity. A Felkin-Ahn model is proposed for the generation of the new stereocenter (C-4) whose absolute configuration has been established as S by X-Ray analysis.

  DOI：

  10.1016/0957-4166(95)00094-6
• 作为产物：
  描述：

  双丙酮-D-甘露糖醇 在 哌啶 sodium periodate 作用下， 以 甲醇 、 水 、 甲苯 为溶剂， 反应 3.5h， 生成 2-[1-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-meth-(Z)-ylidene]-3-oxo-butyric acid methyl ester
  参考文献：
  名称：

  Michael addition of malononitrile to chiral α-acylacrylates

  摘要：

  Starting from 2,3-0-isopropylidene-D-glyceraldehyde (1), 3-O-methyl and 3-O-benzyl-1,2-O-isopropylidene-alpha-D-xylo-pentodialdo-1,4-furanose (4a, 4b), we describe the synthesis of the alpha-acyl-beta-alkyl substituted acrylates 2 and 5. The Michael addition of malononitrile to these substrates gives the polyfunctionalized 2-amino-4H-pyrans 3 and 6 with moderate diastereoselectivity and reasonable overall yield from diols 7 and 8a,b. A detailed analysis is performed scanning different type of bases in the Michael reaction. We find that, while for acceptor 2 no changes are observed, for compound 5 the stereochemical outcome of the 1,4-addition is reversed in going from piperidine, sodium hydride or potassium t-butoxide to lithium diisopropylamide or lithium diisopropylamide/magnesium iodide reagent. Several models for rationalising the results are proposed.

  DOI：

  10.1016/s0040-4020(01)87984-9

文献信息

• The first asymmetric synthesis of polyfunctionalized 4H-pyrans via Michael addition of malononitrile to 2-acyl acrylates
  作者：Rafael González、Nazario Martín、Carlos Seoane、JoséL Marco、Armando Albert、Félix H Cano

  DOI：10.1016/0040-4039(92)80031-e

  日期：1992.6

  Starting from (R)-2,3-O-isopropylideneglyceraldehyde, the first asymmetric synthesis of 4H-pyrans (4BAR) has been developed; a de tailed X-ray structural and stereochemical study has established as R the absolute configuration at the new stereocenter in compounds 4.