(4S)-3-[(2R,3R)-2,4-dimethyl-3-hydroxy-1-oxo-1-pentyl]-4-phenylmethyl-1,3-oxazolidin-2-one | 131899-77-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4S)-3-[(2R,3R)-2,4-dimethyl-3-hydroxy-1-oxo-1-pentyl]-4-phenylmethyl-1,3-oxazolidin-2-one
• 英文别名: (S)-4-benzyl-3-((2R,3R)-3-hydroxy-2,4-dimethylpentanoyl)oxazolidin-2-one；(4S)-4-benzyl-3-[(2R,3R)-3-hydroxy-2,4-dimethylpentanoyl]-1,3-oxazolidin-2-one
• CAS: 131899-77-9
• 化学式: C₁₇H₂₃NO₄
• 分子量: 305.374
• InChiKey: ZPDSPVBRLMOVJJ-VHDGCEQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  66.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4S)-3-[(2R,3R)-2,4-dimethyl-3-hydroxy-1-oxo-1-pentyl]-4-phenylmethyl-1,3-oxazolidin-2-one 在 palladium on activated charcoal 2,6-二甲基吡啶 、 三乙基硅烷 、 正丁基锂 、 二甲基氯化铝 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 丙酮 为溶剂， 反应 3.59h， 生成 (4R,5S,6R)-6-[(tert-butyldimethylsilyl)oxy]-4-hydroxy-5,7-dimethyl-2-octanone
  参考文献：
  名称：

  二甲基氯化铝和甲基二氯化铝的卓越螯合能力。α-和β-立体中心在螯合控制的羰基加成反应中与烯醇硅烷和氢化物亲核试剂的合并立体化学影响

  摘要：

  介绍了在有利于螯合控制的条件下进行的非手性未取代烯醇硅烷和手性 β-羟基醛的路易斯酸促进 (Mukaiyama) 羟醛反应的立体选择性的系统研究。β-烷氧基和β-甲硅烷氧基醛的烯醇硅烷醛醇反应可以实现良好的立体控制，仅带有一个α-或β-立体中心。对α,β-二取代醛的螯合中间体的检查得出结论，syn 醛非对映异构体具有立体中心的排列，其中α-和β-取代基赋予醛羰基增强的面偏向性。因此观察到合成醛的羟醛反应以均匀优异的非对映面选择性进行。

  DOI：

  10.1021/ja011337j
• 作为产物：
  描述：

  (S)-4-苄基-2-唑烷酮 在 chromium dichloride 、 lithium iodide 作用下， 以 四氢呋喃 为溶剂， 生成 (4S)-3-[(2R,3R)-2,4-dimethyl-3-hydroxy-1-oxo-1-pentyl]-4-phenylmethyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  The chromium-Reformatsky reaction: anti-selective Evans-type aldol reactions with excellent inverse induction at ambient temperature

  摘要：

  anti-Aldol products are available in a two step, one pot reaction of 4-substituted oxazolidone, 2-bromopropionyl halide, chromium dichloride and an aldehyde. The diastereofacial selection (induction) is opposite to those of boron Evans enolates, i.e. the unusual ''non-Evans'' anti-aldol products are formed in excellent excess and yield - without base and at room temperature. In contrast to our previous assumptions alpha-unsubstituted acetyloxazolidones do give the Evans-type beta-anti-products preferentially. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00952-0

文献信息

• Lithium Amino Alkoxide–Evans Enolate Mixed Aggregates: Aldol Addition with Matched and Mismatched Stereocontrol
  作者：Janis Jermaks、Evan H. Tallmadge、Ivan Keresztes、David B. Collum

  DOI：10.1021/jacs.7b13776

  日期：2018.2.28

  Building on structural and mechanistic studies of lithiated enolates derived from acylated oxazolidinones (Evans enolates) and chiral lithiated amino alkoxides, we found that amino alkoxides amplify the enantioselectivity of aldol additions. The pairing of enantiomeric series affords matched and mismatched stereoselectivities. The structures of mixed tetramers showing 2:2 and 3:1 (alkoxide-rich) stoichiometries

  在对衍生自酰化恶唑烷酮（Evans 烯醇盐）和手性锂化氨基醇盐的锂化烯醇化物的结构和机理研究的基础上，我们发现氨基醇盐增强了醛醇加成的对映选择性。对映体系列的配对提供匹配和不匹配的立体选择性。显示 2:2 和 3:1（富含醇盐）化学计量的混合四聚体的结构是通过光谱确定的。速率和计算研究基于 3:1 混合四聚体的直接反应提供了可行的机械和立体化学模型，但它们对 2:2 混合聚集体提出了未解决的问题。
• A Useful Modification of the Evans Magnesium Halide Catalyzed anti-Aldol Reaction: Application to Enolizable Aldehydes
  作者：Thomas Hoye、Aaron May、Nathan Connell、Heidi Dahlmann

  DOI：10.1055/s-0030-1258480

  日期：2010.8

  A practical protocol for use of the magnesium halide-catalyzed anti-aldol reaction of an Evans N-acyloxazolidinone with enolizable aldehydes is reported. The yields of anti-aldol adducts for saturated or unsaturated and branched or unbranched aliphatic aldehydes are preparatively useful.

  报道了使用卤化镁催化的 Evans N-酰基恶唑烷酮与烯醇化醛的抗醛醇反应的实用方案。饱和或不饱和和支化或未支化脂族醛的抗醛醇加合物的产率是有用的。
• A short and efficient synthesis of (+)-prelactone B
  作者：Luiz C. Dias、Leonardo J. Steil、Valéria de A. Vasconcelos

  DOI：10.1016/j.tetasy.2003.10.032

  日期：2004.1

  The asymmetric total synthesis of (+)-prelactone B, a biologically important natural beta-hydroxy-delta-lactone derivative that contains a 2,3-trans-dialkylpyran ring system, is described. This approach involves the use of a very efficient oxazolidinone-mediated anti-aldol reaction, and a diastereoselective coupling between a ketene silyl acetal with an aldehyde followed by lactonization. (C) 2003 Elsevier Ltd. All rights reserved.
• The Exceptional Chelating Ability of Dimethylaluminum Chloride and Methylaluminum Dichloride. The Merged Stereochemical Impact of α- and β-Stereocenters in Chelate-Controlled Carbonyl Addition Reactions with Enolsilane and Hydride Nucleophiles
  作者：David A. Evans、Brett D. Allison、Michael G. Yang、Craig E. Masse

  DOI：10.1021/ja011337j

  日期：2001.11.1

  beta-disubstituted aldehydes concludes that the syn aldehyde diastereomer possesses the arrangement of stereocenters wherein the alpha- and beta-substituents impart a reinforcing facial bias upon the aldehyde carbonyl. Aldol reactions of syn aldehydes were thus observed to proceed with uniformly excellent diastereofacial selectivity. Aldol reactions of the corresponding anti aldehydes containing opposing

  介绍了在有利于螯合控制的条件下进行的非手性未取代烯醇硅烷和手性 β-羟基醛的路易斯酸促进 (Mukaiyama) 羟醛反应的立体选择性的系统研究。β-烷氧基和β-甲硅烷氧基醛的烯醇硅烷醛醇反应可以实现良好的立体控制，仅带有一个α-或β-立体中心。对α,β-二取代醛的螯合中间体的检查得出结论，syn 醛非对映异构体具有立体中心的排列，其中α-和β-取代基赋予醛羰基增强的面偏向性。因此观察到合成醛的羟醛反应以均匀优异的非对映面选择性进行。
• The chromium-Reformatsky reaction: anti-selective Evans-type aldol reactions with excellent inverse induction at ambient temperature
  作者：Tobias Gabriel、Ludger Wessjohann

  DOI：10.1016/s0040-4039(97)00952-0

  日期：1997.6

  anti-Aldol products are available in a two step, one pot reaction of 4-substituted oxazolidone, 2-bromopropionyl halide, chromium dichloride and an aldehyde. The diastereofacial selection (induction) is opposite to those of boron Evans enolates, i.e. the unusual ''non-Evans'' anti-aldol products are formed in excellent excess and yield - without base and at room temperature. In contrast to our previous assumptions alpha-unsubstituted acetyloxazolidones do give the Evans-type beta-anti-products preferentially. (C) 1997 Elsevier Science Ltd.