syn-(4S,2'S,3'R)-3-(2'-azido-3'-hydroxy-3'-phenyl-propionyl)-4-(1-methylethyl)-2-oxazolidinone | 151003-65-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: syn-(4S,2'S,3'R)-3-(2'-azido-3'-hydroxy-3'-phenyl-propionyl)-4-(1-methylethyl)-2-oxazolidinone
• 英文别名: (4S)-3-[(2S,3R)-2-azido-3-hydroxy-3-phenylpropanoyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 151003-65-5
• 化学式: C₁₅H₁₈N₄O₄
• 分子量: 318.332
• InChiKey: GOHBYNANJLQNDI-FRRDWIJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  81.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  syn-(4S,2'S,3'R)-3-(2'-azido-3'-hydroxy-3'-phenyl-propionyl)-4-(1-methylethyl)-2-oxazolidinone 在 palladium on activated charcoal 锂硼氢 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 13.0h， 生成 (1R,2R)-(-)-2-氨基-1-苯基-1,3-丙二醇
  参考文献：
  名称：

  Stereoselective syntheses of (−)-chloramphenicol and (+)-thiamphenicol

  摘要：

  Chloramphenicol and thiamphenicol have been enantioselectively synthesized using an asymmetric halohydrin reaction as a key step. In particular, halomethoxylation reaction was used, where O-methyl functions as a hydroxyl protecting group and eliminates an additional protection step. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.07.014
• 作为产物：
  描述：

  anti-(4S,2'S,3'S)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以89%的产率得到syn-(4S,2'S,3'R)-3-(2'-azido-3'-hydroxy-3'-phenyl-propionyl)-4-(1-methylethyl)-2-oxazolidinone
  参考文献：
  名称：

  Stereoselective syntheses of (−)-chloramphenicol and (+)-thiamphenicol

  摘要：

  Chloramphenicol and thiamphenicol have been enantioselectively synthesized using an asymmetric halohydrin reaction as a key step. In particular, halomethoxylation reaction was used, where O-methyl functions as a hydroxyl protecting group and eliminates an additional protection step. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.07.014

文献信息

• Chelation control in metal-assisted aldol addition reactions of .alpha.-N-halogenated imide enolates leading to predominantly anti stereoselectivity. An example of a stereocontrolled Darzens reaction
  作者：Lendon N. Pridgen、Ahmed F. Abdel-Magid、I. Lantos、Susan Shilcrat、Drake S. Eggleston

  DOI：10.1021/jo00071a020

  日期：1993.9

  The aldol reaction of enantiopure N-(haloacetyl)-2-oxazolidinone enolates with aromatic aldehydes was studied for conditions that would induce the reaction to yield predominantly anti adducts. It was found herein that the inherent steric and stereoelectronic properties of the aldehyde (R), as well as its chelative ability with the enolate countercation, are crucial in determining which of its enantiotopic faces reacts. Certain metallic enolates (Sn,IV Zn, and Li) are postulated to react through a three-point coordination transition state to yield mainly anti adducts, while others (Sn,II B, Ti) are shown to react via noncoordinated transition states to yield either syn or anti adducts. X-ray crystallography was instrumental in fully defining the absolute stereochemistry of each product, providing insight into the mechanisms of stereocontrol. The major anti producing pathway for reaction of aromatic aldehydes is postulated to proceed via boatlike or a high-energy ''unfavored chair'' transition state (TS). Finally, using our protocol of varying either the enolate countercation or the substitution pattern on the aromatic aldehyde, we demonstrate how one may synthesize three of the four possible stereoisomers available from this aldol-type reaction, the syn Li isomers 7 being the only inaccessible isomer as a major product in this alpha-halo-2-oxazolidinone system. The anti halohydrins were converted stereospecifically to the trans epoxy esters or epoxy amides in high enantiomeric purity.