(4S)-4-hydroxymethyl-N-[(αR)-α-methylbenzyl]-2-oxazolidinone | 252351-21-6

• 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)-4-hydroxymethyl-N-[(αR)-α-methylbenzyl]-2-oxazolidinone
• 英文别名: (4S,αR)-4-hydroxymethyl-3-(α-methylbenzyl)-2-oxazolidinone；(4S,αR)-4-hydroxymethyl-3-α-methylbenzyl-2-oxazolidinone；(4S)-4-hydroxymethyl-3-((R)-α-methylbenzyl)-2-oxazolidinone；(4S)-4-(hydroxymethyl)-3-[(1R)-1-phenylethyl]-1,3-oxazolidin-2-one
• CAS: 252351-21-6
• 化学式: C₁₂H₁₅NO₃
• 分子量: 221.256
• InChiKey: SZSIMUUQQUCTHP-KOLCDFICSA-N

物化性质

• 沸点：
  444.4±28.0 °C(Predicted)
• 密度：
  1.219±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4S)-4-hydroxymethyl-N-[(αR)-α-methylbenzyl]-2-oxazolidinone 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 (4R)-4-hydroxymethyl-N-[(αR)-α-methylbenzyl]-2-oxazolidinone
  参考文献：
  名称：

  A novel dynamic kinetic resolution accompanied by intramolecular transesterification: asymmetric synthesis of a 4-hydroxymethyl-2-oxazolidinone from serinol derivatives

  摘要：

  Reaction paths of the one-pot reaction of (R)-2-(alpha-methylbenzyl)amino-1,3-propanediol (1) and 2-chloroethyl chloroformate with DBU giving (4S,alphaR)-4-hydroxymethyl-3-(alpha-methylbenzyl)-2-oxazolidinone [(4S)-2] (94% de) were investigated. Intermediates of this reaction, 2-chloroethyl (2S)- and 2-chloroethyl (2R)-3-hydroxy-2-[(alphaR)-alpha-methylbenzyl]aminopropyl carbonates [(2S)-4 and (2R)-4], were synthesized individually. After the addition of DBU to the respective solution of the carbonate (2S)-4 and that of (2R)-4 in dichloromethane, the intramolecular transesteritication between (2S)-4 and (2R)-4 and the diastereoselective intramolecular cyclization proceeded to afford (4S)-2 in high diastereomeric excess. Therefore, two monocarbonates (2S)-4 and (2R)-4 were kinetically resolved by this cyclization during the intramolecular transesterification between (2S)-4 and (2R)-4. We found that this process involved dynamic kinetic resolution accompanied by intramolecular transesterification. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00477-0
• 作为产物：
  描述：

  (R)-2-[(α-methylbenzyl)amino]-1,3-propanediol 在 吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 氘代氯仿 、 二氯甲烷 为溶剂， 反应 72.0h， 生成 (4S)-4-hydroxymethyl-N-[(αR)-α-methylbenzyl]-2-oxazolidinone
  参考文献：
  名称：

  Asymmetric synthesis of the 4-hydroxymethyl-2-oxazolidinone from the serinol derivative and chloroformates

  摘要：

  Asymmetric desymmetrization of 2-[(alpha R)-alpha-methylbenzyl]amino-1,3-propanediol (1) with 2-chloroethyl chloroformate and DBU at room temperature gave optically active (4S)-4-hydroxymethyl-N-[(alphaR)-alpha-methylbenzyl]-2-oxazolidinone [(4S)-2] (up to 94% de). This reaction involves kinetic resolution and [1,3]-alkoxyacyl migration of 2-chloroethyl (2S)- and 2-chloroethyl (2R)-3-hydroxy-2-[(alpha R)-alpha-methylbenzyl]aminopropyl carbonates [(2S)-4 and (2R)-4]. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01548-8

文献信息

• Diastereoselective intramolecular acyl transfer of 5-(α-methylbenzyl)amino-1,3-dioxan-2-one to 4-hydroxymethyl-2-oxazolidinones
  作者：Shigeo Sugiyama、Haruka Fukuchi、Keitaro Ishii

  DOI：10.1016/j.tet.2007.09.004

  日期：2007.11

  Intramolecular acyl transfer of (R)-5-(alpha-methylbenzyl)amino-1,3-dioxan-2-one (2) by treatment with DBU in CD2Cl2, CDCl3, C6D6, CD3CN, CD3NO2, DMSO-d(6), DMF, THF-d(8), (PrOH)-Pr-i, and (BuOH)-Bu-t at room temperature afforded (4S,alpha R)-4-hydroxymethyl-3-alpha-methyl-benzyl-2-oxazolidinone [(4S)-3] in moderate to quantitative yields with 58-94% de via an asymmetric desymmetrization process. Treatment of 2 with DBU and Cs2CO3 in MeOH and EtOH gave (4S)-3 and (4R)-3 without diastereoselectivities. Acidic treatment of 2 using HCO2H, AcOH, EtCO2H, (PrCO2H)-Pr-i, (BuCO2H)-Bu-t, and C6F5OH in CDCl3 gave (4S)-3 in moderate diastereoselectivities (26-52% de). First-order kinetics were observed in the reaction of 2 to (4S)-3 with DBU in CDCl3 and THF-d(8). (C) 2007 Elsevier Ltd. All rights reserved.
• Studies on two different diastereoselective reaction pathways from a serinol derivative to 4-hydroxymethyl-2-oxazolidinones using 2-chloroethyl chloroformate and N,N′-disuccinimidyl carbonate
  作者：Shigeo Sugiyama、Keitaro Ishii

  DOI：10.1016/j.tetasy.2010.11.022

  日期：2010.12

  Two reaction pathways and their diastereoselectivity-determining steps of the asymmetric desymmetrization of (R)-2-(alpha-methylbenzyl)amino-1,3-propanediol 1 with 2-chloroethyl chloroformate (CCF) and with N,N'-disuccinimidyl carbonate giving (4S,alpha R)-4-hydroxymethyl-3-alpha-methylbenzyl-2-oxazolidinones (4S)-3 and its (4R,alpha R)-diastereomer (4R)-3 were investigated. The reaction of serinol 1 and CCF to give the corresponding carbonates was not a diastereoselectivity-determining step. The carbonates gave (R)-5-(alpha-methylbenzyl)amino-1,3-dioxan-2-one 4 after addition of DBU, and an intramolecular acyl transfer of 4 was found to be a diastereoselectivity-determining step to give (4S)-3. Conversely, the reaction of serinol 1 and N,N'-disuccinimidyl carbonate afforded directly the opposite diastereomer (4R)-3 but not via the intermediate 4. Thus, their diastereoselectivities depended on the acylating reagent. (C) 2010 Elsevier Ltd. All rights reserved.
• Total synthesis of (R)-(−)-actisonitrile via O-alkylation of optically active 4-hydroxymethyloxazolidin-2-one derivative
  作者：Shigeo Sugiyama、Akihiro Ishida、Moeko Tsuchida、Keitaro Ishii

  DOI：10.1016/j.tetasy.2011.11.002

  日期：2011.11

  The enantioselective synthesis of (R)-(-)-actisonitrile 1 has been achieved via O-alkylation of (4R,alpha S)-4-hydroxymethyl-3-(alpha-methylbenzyl)oxazolidin-2-one (alpha S)-4 with 1-iodohexadecane in the presence of CsOH in DMF. Under these reaction conditions, the O-alkylation was much faster than the intramolecular acyl transfer of (alpha S)-4. (C)2011 Elsevier Ltd. All rights reserved.
• Asymmetric synthesis of the 4-hydroxymethyl-2-oxazolidinone from the serinol derivative and chloroformates
  作者：Shigeo Sugiyama、Shoko Watanabe、Keitaro Ishii

  DOI：10.1016/s0040-4039(99)01548-8

  日期：1999.10

  Asymmetric desymmetrization of 2-[(alpha R)-alpha-methylbenzyl]amino-1,3-propanediol (1) with 2-chloroethyl chloroformate and DBU at room temperature gave optically active (4S)-4-hydroxymethyl-N-[(alphaR)-alpha-methylbenzyl]-2-oxazolidinone [(4S)-2] (up to 94% de). This reaction involves kinetic resolution and [1,3]-alkoxyacyl migration of 2-chloroethyl (2S)- and 2-chloroethyl (2R)-3-hydroxy-2-[(alpha R)-alpha-methylbenzyl]aminopropyl carbonates [(2S)-4 and (2R)-4]. (C) 1999 Elsevier Science Ltd. All rights reserved.
• A novel dynamic kinetic resolution accompanied by intramolecular transesterification: asymmetric synthesis of a 4-hydroxymethyl-2-oxazolidinone from serinol derivatives
  作者：Shigeo Sugiyama、Shoko Watanabe、Takayuki Inoue、Rie Kurihara、Takahiro Itou、Keitaro Ishii

  DOI：10.1016/s0040-4020(03)00477-0

  日期：2003.5

  Reaction paths of the one-pot reaction of (R)-2-(alpha-methylbenzyl)amino-1,3-propanediol (1) and 2-chloroethyl chloroformate with DBU giving (4S,alphaR)-4-hydroxymethyl-3-(alpha-methylbenzyl)-2-oxazolidinone [(4S)-2] (94% de) were investigated. Intermediates of this reaction, 2-chloroethyl (2S)- and 2-chloroethyl (2R)-3-hydroxy-2-[(alphaR)-alpha-methylbenzyl]aminopropyl carbonates [(2S)-4 and (2R)-4], were synthesized individually. After the addition of DBU to the respective solution of the carbonate (2S)-4 and that of (2R)-4 in dichloromethane, the intramolecular transesteritication between (2S)-4 and (2R)-4 and the diastereoselective intramolecular cyclization proceeded to afford (4S)-2 in high diastereomeric excess. Therefore, two monocarbonates (2S)-4 and (2R)-4 were kinetically resolved by this cyclization during the intramolecular transesterification between (2S)-4 and (2R)-4. We found that this process involved dynamic kinetic resolution accompanied by intramolecular transesterification. (C) 2003 Elsevier Science Ltd. All rights reserved.