syn-(4S,2'S,3'R)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone | 127118-30-3

• 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: syn-(4S,2'S,3'R)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone
• 英文别名: (4S)-3-[(2S,3R)-2-bromo-3-hydroxy-3-phenylpropanoyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 127118-30-3
• 化学式: C₁₅H₁₈BrNO₄
• 分子量: 356.216
• InChiKey: SDIFBHFIISBFMN-FRRDWIJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  syn-(4S,2'S,3'R)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone 在 sodium azide 作用下， 以 二甲基亚砜 为溶剂， 生成 (4S)-3-[(2R,3R)-2-azido-3-hydroxy-3-phenylpropanoyl]-4-propan-2-yl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00071a020
• 作为产物：
  描述：

  (+)-(4S)-3-bromoacetyl-4-(1-methylethyl)-2-oxazolidinone 、 苯甲醛 以67%的产率得到
  参考文献：
  名称：

  PRIDGEN, LENDON N.;ABDEL-MAGID, A.;LANTOS, I., TETRAHEDRON LETT., 30,(1989) N1, C. 5539-5542

  摘要：

  DOI：

文献信息

• A predominately anti-stereoselective chiral metal directed aldol condensation with aromatic aldehydes
  作者：Lendon N. Pridgen、A. Abdel-Magid、I. Lantos

  DOI：10.1016/s0040-4039(01)93794-3

  日期：1989.1

  Chiral haloacetyl oxazolidinones were reacted with aromatic aldehydes via their kinetically generated Z-enolates to yield predominately anti aldol adducts. The reaction is postulated to proceed thru a boat-like transition state. A unique reversal of chirality was observed in using stannous enolates.

  手性卤代乙酰基恶唑烷酮通过其动力学生成的Z-烯酸酯与芳族醛反应，主要生成抗羟醛加合物。假定反应通过船状过渡态进行。在使用亚锡烯醇酸酯时观察到独特的手性逆转。
• PRIDGEN, LENDON N.;ABDEL-MAGID, A.;LANTOS, I., TETRAHEDRON LETT., 30,(1989) N1, C. 5539-5542
  作者：PRIDGEN, LENDON N.、ABDEL-MAGID, A.、LANTOS, I.

  DOI：——

  日期：——
• 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.