(R,S)-5-hexanoyloxymethyl-3-tert-butyl-oxazolidin-2-one | 93462-84-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (R,S)-5-hexanoyloxymethyl-3-tert-butyl-oxazolidin-2-one
• 英文别名: 5-hexanoyloxymethyl-tert-butyl-2-oxazolidinone；(3-Tert-butyl-2-oxo-1,3-oxazolidin-5-YL)methyl hexanoate
• CAS: 93462-84-1
• 化学式: C₁₄H₂₅NO₄
• 分子量: 271.357
• InChiKey: NJOCYWBZBKWZNA-UHFFFAOYSA-N

物化性质

• 沸点：
  396.0±15.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R,S)-5-hexanoyloxymethyl-3-tert-butyl-oxazolidin-2-one 在 sodium hydroxide 、 lipoprotein lipase Amano 3 adsorbed on Amberlite XAD-7 、 水 、 氢溴酸 、 sodium methylate 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 26.0h， 生成 (R)-3-N-ethoxycarbonyl-N-tert-butylamino-1,2-epoxypropane
  参考文献：
  名称：

  Biological resolution of racemic 2-oxazolidinones. Part VI. Stereochemical inversion of (R)-5-hydroxymethyl-3-tert-butyl-2-oxazolidinone or (R)-5-hydroxymethyl-3-isopropyl-2-oxazolidinone to the corresponding (S)-isomer.

  摘要：

  (R)-5-羟甲基-3-叔丁基-2-恶唑烷酮（1a）或(R)-5-羟甲基-3-异丙基-2-恶唑烷酮（1b）的立体化学反转，通过关键中间体(R)-3-N-乙氧羰基-N-叔丁基氨基-1,2-环氧丙烷（5a）或(R)-3-N-乙氧羰基-N-异丙基氨基-1,2-环氧丙烷（5b），以高对映体过量成功转化为相应的(S)-异构体。因此，分别从相应的(R)-异构体（1a；99% e.e.，1b；95% e.e.）得到了(S)-1a（99% e.e.）或(S)-1b（97% e.e.）。

  DOI：

  10.1271/bbb1961.49.1669

文献信息

• Asymmetric Hydrolysis of Racemic 2-Oxazolidinone Esters with Lipases
  作者：Shigeki Hamaguchi、Masanori Asada、Junzo Hasegawa、Kiyoshi Watanabe

  DOI：10.1080/00021369.1984.10866481

  日期：1984.9.1

  The enzymatic hydrolysis of (R, S)-5-acyloxymethyl-3-alkyl-oxazolidin-2-one I and the behavior of (S)-I for extraction with an organic solvent were examined so as to extend the biological resolution to racemates, and to learn about more appropriate combinations of substrates with lipases on the asymmetric hydrolysis. The combination of (R, S)-5-hexanoyloxymethyl-3-tert-butyl-oxazolidin-2-one 4 with lipoprotein lipase Amano 3 (L. P. L. Amano 3, origin; Pseudomonas aeruginosa) and that of (R, S)-5-octanoyloxymethyl-3-isopropyl-oxazolidin-2-one 14 with L. P. L. Amano 3 efficiently gave (S)-5-hydroxymethyl-3-tert-butyl-oxazolidin-2-one (S)-lla (99% e.e.) and (S)-5-hydroxymethyl-3-isopropyl-oxazolidin-2-one (S)-IIb (99% e.e.),respectively. (S)-IIa and (S)-IIb could be considered to be favorable intermediates for preparing optically active β-blockers.

  研究了(R, S)-5-己酰氧基甲基-3-烷基-恶唑啉-2-酮 I 的酶水解以及 (S)-I 用有机溶剂萃取的行为，以便将生物分辨率扩展到外消旋体，并了解底物与脂肪酶在不对称水解中的更合适组合。(R,S)-5-己酰氧甲基-3-叔丁基-噁唑烷-2-酮 4 与脂蛋白脂肪酶天野 3（L. P. L. Amano 3，原产地；铜绿假单胞菌）的组合，以及(R,S)-5-辛酰氧甲基-3-异丙基-噁唑烷-2-酮 14 与 L. P. L. Amano 3 的组合，都能有效地水解脂蛋白脂肪酶。P. L. Amano 3 分别有效地得到了(S)-5-羟甲基-3-叔丁基-噁唑烷-2-酮(S)-lla (99% e.e.)和(S)-5-羟甲基-3-异丙基-噁唑烷-2-酮(S)-IIb (99% e.e.)。(S)-IIa和(S)-IIb可被视为制备光学活性β-受体阻滞剂的有利中间体。
• Biological resolution of racemic 2-oxazolidinones. Part V. Stereospecific hydrolysis of 2-oxazolidinone esters and separation of products with an immobilized lipase column.
  作者：Shigeki HAMAGUCHI、Masanori ASADA、Junzo HASEGAWA、Kiyoshi WATANABE

  DOI：10.1271/bbb1961.49.1661

  日期：——

  Hydrophobic (R, S)-5-acyloxymethyl-3-alkyl-2-oxazolidinones were successfully hydrolyzed stereospecifically with lipoprotein lipase Amano 3 (LPL) adsorbed on Amberlite XAD-7. The LPL immobilized on the resin was not desorbed on washing with phosphate buffer, toluene or hexane. The activity loss of the column was little during storage for five months at room temperature. Stereospecific hydrolyses were performed pulsewise with the column, and separation of the hydrophobic (S)-ester from the hydrophilic (R)-alcohol was also performed on the same column utilizing the hydrophobic interaction between the (S)-ester and the support resin. The immobilized LPL column was stable on repetition of these operations for over 20 times. The optical purities of the obtained (S)-oxazolidinones, which were favorable intermediates for the synthesis of (S)-β-blockers, were 96-98% e.e.

  用吸附在 Amberlite XAD-7 上的脂蛋白脂肪酶天野 3（LPL）成功地立体定向水解了疏水性（R，S）-5-乙酰氧基甲基-3-烷基-2-恶唑烷酮。用磷酸盐缓冲液、甲苯或正己烷洗涤时，固定在树脂上的 LPL 不会解吸。在室温下储存五个月后，色谱柱的活性损失很小。利用该色谱柱进行了立体特异性水解，并在同一色谱柱上利用(S)-酯和支撑树脂之间的疏水作用分离了疏水的(S)-酯和亲水的(R)-醇。固定化 LPL 色谱柱在重复上述操作 20 多次后保持稳定。获得的(S)-噁唑烷酮是合成(S)-β-受体阻滞剂的有利中间体，其光学纯度为 96-98%。
• KAN, KAZUNORI;MIYAMA, AKIMASA;HAMAGUCHI, SHIGEKI;OHASHI, TAKEHISA;WATANAB+, AGR. AND BIOL. CHEM., 1985, 49, N 6, 1669-1674
  作者：KAN, KAZUNORI、MIYAMA, AKIMASA、HAMAGUCHI, SHIGEKI、OHASHI, TAKEHISA、WATANAB+

  DOI：——

  日期：——
• Biological resolution of racemic 2-oxazolidinones. Part VI. Stereochemical inversion of (R)-5-hydroxymethyl-3-tert-butyl-2-oxazolidinone or (R)-5-hydroxymethyl-3-isopropyl-2-oxazolidinone to the corresponding (S)-isomer.
  作者：Kazunori KAN、Akimasa MIYAMA、Shigeki HAMAGUCHI、Takehisa OHASHI、Kiyoshi WATANABE

  DOI：10.1271/bbb1961.49.1669

  日期：——

  The Stereochemical inversion of (R)-5-hydroxymethyl-3-tert-butyl-2-oxazolidinone (1a) or (R)-5-hydroxymethyl-3-isopropyl-2-oxazohdinone (1b) to the corresponding (S)-isomer was accomplished via a key intermediate, (R)-3-N-ethoxycarbonyl-N-tert-butylamino-1, 2-epoxypropane (5a) or (R)-3-N-ethoxycarbonyl-N-isopropylamino-1, 2-epoxypropane (5b), in a high enantiomeric excess. (S)-1a (99% e.e.) or (S)-1b (97% e.e.) was thus obtained from the respective (R)-isomer (1a; 99% e.e., 1b; 95% e.e.).

  (R)-5-羟甲基-3-叔丁基-2-恶唑烷酮（1a）或(R)-5-羟甲基-3-异丙基-2-恶唑烷酮（1b）的立体化学反转，通过关键中间体(R)-3-N-乙氧羰基-N-叔丁基氨基-1,2-环氧丙烷（5a）或(R)-3-N-乙氧羰基-N-异丙基氨基-1,2-环氧丙烷（5b），以高对映体过量成功转化为相应的(S)-异构体。因此，分别从相应的(R)-异构体（1a；99% e.e.，1b；95% e.e.）得到了(S)-1a（99% e.e.）或(S)-1b（97% e.e.）。