anti-(4S,2'R,3'R)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone | 127181-71-9

• 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: anti-(4S,2'R,3'R)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone
• 英文别名: (4S)-3-[(2R,3R)-2-bromo-3-hydroxy-3-phenylpropanoyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 127181-71-9
• 化学式: C₁₅H₁₈BrNO₄
• 分子量: 356.216
• InChiKey: SDIFBHFIISBFMN-JHJVBQTASA-N

物化性质

• 沸点：
  487.2±45.0 °C(Predicted)
• 密度：
  1.486±0.06 g/cm3(Predicted)

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：

  anti-(4S,2'R,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 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：

  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)-4-isopropyl-3-[(2E)-3-phenylprop-2-enoyl]-1,3-oxazolidin-2-one 在 溴 、 硝酸 、 silver(l) oxide 作用下， 以 水 、 丙酮 为溶剂， 反应 0.5h， 生成 anti-(4S,2'R,3'R)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone 、 anti-(4S,2'S,3'S)-3-(3'-Hydroxy-3'-phenyl-2'-bromo-1'-oxopropyl)-4-(1-methylethyl)-2-oxazolidinone
  参考文献：
  名称：

  银（I）促进的手性N-烯酰基-2-恶唑烷酮的不对称卤代醇反应：范围和局限性

  摘要：

  在卤素（Br 2 / I 2）和水（银）促进的有机溶剂中，手性N-烯丙基-2-恶唑烷酮1的卤代醇反应可以高效地进行，具有高的抗和区域选择性，并且具有中等至良好的非对映选择性。链烯酰基，肉桂酰基和缺电子的肉桂酰基底物在丙酮水溶液中顺利进行溴代醇反应，但没有碘代醇反应，其中富电子的肉桂酰基底物优选在丙酮水溶液中进行碘代醇反应，在THF水溶液中观察到中等的非对映选择性和非对映选择性增强。

  DOI：

  10.1016/j.tet.2005.01.053

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。
• Lewis acid catalyzed asymmetric halohydrin reactions of chiral α,β-unsaturated carboxylic acid derivatives with N-halosuccinimide (NXS) as the halogen source
  作者：Saumen Hajra、Manishabrata Bhowmick、Ananta Karmakar

  DOI：10.1016/j.tetlet.2005.03.014

  日期：2005.4

  Lewis acid catalyzed asymmetric halohydrin reactions—(halohydroxylation as well as halomethoxylation) of chiral α,β-unsaturated carboxylic acid derivatives were performed using N-halosuccinimide (NXS; X = Br, I) as the halogen source. Regio- and anti-selectivity of 100% and moderate to good diastereoselectivity with good yields were observed when Oppolzer’s sultam was used as the chiral auxiliary.

  使用N-卤代琥珀酰亚胺（NXS; X = Br，I）作为卤素源，进行路易斯酸催化的手性α，β-不饱和羧酸衍生物的不对称卤代醇反应（卤代羟基化以及卤代甲氧基化）。当Oppolzer的sultam用作手性助剂时，观察到区域选择性和抗选择性为100％，中等至良好的非对映选择性，并具有良好的收率。路易斯酸中，Yb（OTf）3被发现是最好的催化剂。烯酰基和肉桂酰基底物顺利地进行了溴代醇反应，较富电子的肉桂酰基底物优选经历了碘代醇反应。但是，缺电子的肉桂酰基底物不响应此路易斯酸催化的NXS与卤代醇反应（X = Cl，Br，I）。
• Silver (I)-promoted asymmetric halohydrin reaction of chiral N-enoyl-2-oxazolidinones: scope and limitations
  作者：Saumen Hajra、Ananta Karmakar、Manishabrata Bhowmick

  DOI：10.1016/j.tet.2005.01.053

  日期：2005.2

  halohydrin reaction of chiral N-enoyl-2-oxazolidinones 1 by halogen (Br2/I2) and water were efficiently carried out in aqueous organic solvent promoted by silver(I) with high anti- and regioselectivity and moderate to good diastereoselectivities. The alkenoyl, cinnamoyl and electron-deficient cinnamoyl substrates smoothly underwent bromohydrin reaction in aqueous acetone but no iodohydrin reaction, where

  在卤素（Br 2 / I 2）和水（银）促进的有机溶剂中，手性N-烯丙基-2-恶唑烷酮1的卤代醇反应可以高效地进行，具有高的抗和区域选择性，并且具有中等至良好的非对映选择性。链烯酰基，肉桂酰基和缺电子的肉桂酰基底物在丙酮水溶液中顺利进行溴代醇反应，但没有碘代醇反应，其中富电子的肉桂酰基底物优选在丙酮水溶液中进行碘代醇反应，在THF水溶液中观察到中等的非对映选择性和非对映选择性增强。
• 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：——
• Stereoselective syntheses of (−)-chloramphenicol and (+)-thiamphenicol
  作者：Saumen Hajra、Ananta Karmakar、Tapan Maji、Amiya Kumar Medda

  DOI：10.1016/j.tet.2006.07.014

  日期：2006.9

  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.