(4S)-3-<(2R,3S)-3-hydroxy-2-methyl-1-oxo-3-phenylpropyl>-4-(1-methylethyl)-2-oxazolidinone | 104758-28-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4S)-3-<(2R,3S)-3-hydroxy-2-methyl-1-oxo-3-phenylpropyl>-4-(1-methylethyl)-2-oxazolidinone
• 英文别名: (4S)-3-[(2R,3S)-3-hydroxy-2-methyl-3-phenylpropionyl]-4-isopropyloxazolidin-2-one；(4S)-3-[(2R,3S)-3-hydroxy-2-methyl-3-phenylpropanoyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 104758-28-3
• 化学式: C₁₆H₂₁NO₄
• 分子量: 291.347
• InChiKey: OEELHKWPTSLBPL-BNOWGMLFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  66.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (S)-4-异丙基-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,3S)-3-hydroxy-2-methyl-1-oxo-3-phenylpropyl>-4-(1-methylethyl)-2-oxazolidinone
  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。
• Asymmetric aldol reactions. Mechanism of solvent effect on stereoselectivity is specific, stoichiometric binding of tetrahydrofuran to a chiral titanium enolate
  作者：Shailaja Shirodkar、Maryellen Nerz-Stormes、Edward R. Thornton

  DOI：10.1016/s0040-4039(00)97710-4

  日期：——

  role in aldol reactions of an acyloxazolidinone-derived titanium enolate. Diethyl ether produces nearly fivefold higher diastereofacial selectivity than THF. We now show that this strong solvent effect arises from stoichiometric binding, most probably to the titanium, of THF in the transition structure, whereas ether is not bound. These mechanistic results indicate that THF lowers the selectivity by interfering

  溶剂在由酰基恶唑烷酮衍生的烯醇钛的醛醇缩合反应中起重要作用。二乙醚的非对映选择性比四氢呋喃高出将近五倍。现在我们表明，这种强溶剂作用是由于过渡结构中THF的化学计量结合（最可能与钛结合）引起的，而醚没有结合。这些机理结果表明，THF通过干扰螯合控制而降低了选择性，这在醚中是高度优选的。暗示包括使用其他醚来进一步改善螯合/非螯合控制的可能性，或者甚至使用手性醚作为手性控制基团或辅助剂。
• Apparent chelation control in aldol reactions of chiral (Me2CHO)3Ti-enolates
  作者：Maryellen Nerz-Stonies、Edward R. Thornton

  DOI：10.1016/s0040-4039(00)84131-3

  日期：1986.1

  Directed aldol reactions of chiral (Me2CHO)3Ti-enolates give the opposite diastereofacial selectivity compared with the corresponding boron enolates. This stereochemical reversal is best explained if the Ti reactions involve chelation (not possible with boron, and previously thought to be unfavorable with (Me2CHO)3Ti-enolates). Changing the solvent from THF to diethyl ether significantly enhances the

  与相应的硼烯醇酸酯相比，手性（Me 2 CHO）3钛烯醇酸酯的直接醛醇缩合反应具有相反的非对面选择性。如果Ti反应涉及螯合（对于硼是不可能的，以前被认为对（Me 2 CHO）3 Ti-烯酸酯不利），则最好解释这种立体化学逆转。将溶剂从THF更改为二乙醚显着增强了假设的螯合效果。因此，使用Ti或硼可以方便地合成任何一种产物对映异构体，从该手性助剂开始，该手性助剂的构型易于并廉价地衍生自天然来源。
• Asymmetric aldol reactions. Use of the titanium enolate of a chiral N-acyloxazolidinone to reverse diastereofacial selectivities
  作者：Maryellen Nerz-Stormes、Edward R. Thornton

  DOI：10.1021/jo00007a042

  日期：1991.3

  Aldol reactions of the titanium enolate of (S)-N-propionyl-4-isopropyl-2-oxazolidinone (readily derived from L-valine) with representative aldehydes give high diastereofacial selectivities for the syn aldol adducts expected from chelation control. This represents a remarkable reversal in selectivity compared with the corresponding boron enolate, thus permitting either enantiomeric form of beta-hydroxy-alpha-methyl carboxylic acids to be made from a single, readily available oxazolidinone simply by changing the metal. A lithium interference effect is shown to be easily prevented by use of excess titanium. Use of diethyl ether as solvent rather than THF significantly enhances the stereoselectivity. Mechanistically, the observed stereochemical reversal constitutes very strong evidence that chelation is operative with titanium, presumably through a chelated chairlike transition structure. In this transition structure, the conformation would be rigidly locked by chelation and the titanium would be at least hexacoordinate, resulting in a ''superaxial'' ligand, thus nicely explaining the high stereocontrol.
• Acyclic stereoselection. 54. Extending the scope of the Evans asymmetric aldol reaction: preparation of anti and "non-Evans" syn aldols
  作者：Michael A. Walker、Clayton H. Heathcock

  DOI：10.1021/jo00020a006

  日期：1991.9

  The Evans reagent, imide 1, reacts with aldehydes under Lewis acid catalysis to give anti or ''non-Evans'' syn aldols 5 or 6, depending on the reaction conditions. This discovery considerably amplifies the synthetic utility of these important reagents for asymmetric synthesis.