2,3-O-isopropylidene-γ-D-ribonolactone 2-methylacetoacetate | 259800-72-1

• 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: 2,3-O-isopropylidene-γ-D-ribonolactone 2-methylacetoacetate
• 英文别名: 2-methylacetoacetate of D-ribonolactone acetonide；[(3aR,6R,6aR)-2,2-dimethyl-4-oxo-6,6a-dihydro-3aH-furo[3,4-d][1,3]dioxol-6-yl]methyl 2-methyl-3-oxobutanoate
• CAS: 259800-72-1
• 化学式: C₁₃H₁₈O₇
• 分子量: 286.282
• InChiKey: CNGNKJVAMIGOEA-JPMHVPNBSA-N

物化性质

• 沸点：
  406.5±45.0 °C(predicted)
• 密度：
  1.215±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3-O-isopropylidene-γ-D-ribonolactone 2-methylacetoacetate 在 titanium(IV) tetraethanolate 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 17.25h， 生成 ethyl (2R)-2-benzyl-2-methyl-3-oxobutanoate
  参考文献：
  名称：

  Asymmetric synthesis of quaternary α-amino acids using d-ribonolactone acetonide as chiral auxiliary

  摘要：

  We describe a new simple methodology to prepare enantiopure alpha,alpha-dialkylglycines based on the use of commercially available D-ribonolactone as a chiral auxiliary. Enantiopure alpha-methyl and alpha-butyl series are prepared through diastereoselective alkylation and subsequent Schmidt rearrangement of alpha,alpha-dialkylacetoacetates of D-ribonolactone acetonide. Absolute configuration was assigned through preparation of enantiopure 4,4-disubstituted 3-methyl-2-pyrazolin-5-ones. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00457-7
• 作为产物：
  描述：

  2,3-O-异亚丙基-D-核糖酸 gamma-内酯 在 potassium carbonate 作用下， 以 丙酮 、 甲苯 为溶剂， 反应 31.0h， 生成 2,3-O-isopropylidene-γ-D-ribonolactone 2-methylacetoacetate
  参考文献：
  名称：

  Asymmetric synthesis of quaternary α-amino acids using d-ribonolactone acetonide as chiral auxiliary

  摘要：

  We describe a new simple methodology to prepare enantiopure alpha,alpha-dialkylglycines based on the use of commercially available D-ribonolactone as a chiral auxiliary. Enantiopure alpha-methyl and alpha-butyl series are prepared through diastereoselective alkylation and subsequent Schmidt rearrangement of alpha,alpha-dialkylacetoacetates of D-ribonolactone acetonide. Absolute configuration was assigned through preparation of enantiopure 4,4-disubstituted 3-methyl-2-pyrazolin-5-ones. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00457-7

文献信息

• The Contribution Made by Triphenylphosphane in the Putative Catalysis by Ruthenium Species in Conjugate Additions of β-Dicarbonyl Compounds
  作者：Maria Lumbierres、Caroline Marchi、Marcial Moreno-Mañas、Rosa M. Sebastián、Adelina Vallribera、Elena Lago、Elies Molins

  DOI：10.1002/1099-0690(200106)2001:12<2321::aid-ejoc2321>3.0.co;2-y

  日期：2001.6

  Triphenylphosphane catalyzes conjugate additions of β-dicarbonyl compounds to π-acceptor olefins and dialkyl azodicarboxylates. Formation of quaternary centers at the nucleophiles has been achieved. The catalytic action of tris(triphenylphosphane)ruthenium(II) chloride and tetrakis(triphenylphosphane)ruthenium(II) hydride is at least partially due to the phosphane ligand.

  三苯基膦催化 β-二羰基化合物与 π-受体烯烃和偶氮二羧酸二烷基酯的共轭加成。已实现在亲核试剂处形成四元中心。三（三苯基膦）氯化钌（II）和四（三苯基膦）氢化钌（II）的催化作用至少部分归因于磷烷配体。
• Electrochemically-initiated Michael addition of chiral acetoacetic derivatives to methyl vinyl ketone: stereocontrolled construction of quaternary carbon centers
  作者：Laura Palombi、Marta Feroci、Monica Orsini、Achille Inesi

  DOI：10.1016/s0957-4166(02)00636-5

  日期：2002.10

  Stereoselective conjugate addition of chiral β-dicarbonyl derivatives to methyl vinyl ketone was promoted by electrolysis, using a catalytic amount of electricity. With respect to the metal-catalyzed methods, the electrochemical, metal-free conditions resulted in enhanced reactivity of the electrogenerated enolates, so that the Michael addition was found to occur under mild conditions and short reaction

  通过催化作用，利用催化量的电，手性β-二羰基衍生物向甲基乙烯基酮的立体选择性共轭加成反应。关于金属催化的方法，电化学，无金属的条件导致电生成的烯醇化物的反应性增强，因此发现迈克尔加成反应在温和的条件下和较短的反应时间下进行，从而提供了具有明显非对映异构体过量的产物。当将Oppolzer的sultam用作手性诱导剂并使用延长的反应时间时，观察到立体选择性的逆转，证明了电化学诱导的加成反应和随后的热力学平衡的动力学控制。基于电化学的方法也被用于精制季生立体碳中心。
• Michael additions catalyzed by phosphines. An overlooked synthetic method
  作者：Carolina Gimbert、Maria Lumbierres、Caroline Marchi、Marcial Moreno-Mañas、Rosa M. Sebastián、Adelina Vallribera

  DOI：10.1016/j.tet.2005.07.005

  日期：2005.9

  Triphenylphosphine and tributylphosphine are excellent catalysts for Michael additions. Many beta-dicarbonyl compounds and electron-poor olefins, including sterically demanding partners, react successfully. The Michael addition catalyzed by phosphines deserves attention in its own right as a useful synthetic method. (c) 2005 Elsevier Ltd. All rights reserved.
• Asymmetric synthesis of quaternary α-amino acids using d-ribonolactone acetonide as chiral auxiliary
  作者：Marcial Moreno-Mañas、Elisenda Trepat、Rosa M. Sebastián、Adelina Vallribera

  DOI：10.1016/s0957-4166(99)00457-7

  日期：1999.10

  We describe a new simple methodology to prepare enantiopure alpha,alpha-dialkylglycines based on the use of commercially available D-ribonolactone as a chiral auxiliary. Enantiopure alpha-methyl and alpha-butyl series are prepared through diastereoselective alkylation and subsequent Schmidt rearrangement of alpha,alpha-dialkylacetoacetates of D-ribonolactone acetonide. Absolute configuration was assigned through preparation of enantiopure 4,4-disubstituted 3-methyl-2-pyrazolin-5-ones. (C) 1999 Elsevier Science Ltd. All rights reserved.