[(2S,3R)-3-Methyloxolan-2-yl]methanol | 18689-91-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: [(2S,3R)-3-Methyloxolan-2-yl]methanol
• CAS: 18689-91-3
• 化学式: C₆H₁₂O₂
• 分子量: 116.16
• InChiKey: BWDPETMQLDMANN-PHDIDXHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (3-methyltetrahydrofuran-2-yl)methyl acetate 在 Burkholderia cepacia lipase 、 水 、 sodium hydroxide 作用下， 以 aq. phosphate buffer 、 丙酮 为溶剂， 反应 1.7h， 以72%的产率得到
  参考文献：
  名称：

  洋葱伯克霍尔德氏菌脂肪酶对γ-丁内酯伯醇的对映和非对映选择性的分子基础

  摘要：

  AbstractBurkholderia cepacia lipase (BCL) shows high enantioselectivity toward chiral primary alcohols, but this enantioselectivity is often unpredictable, especially for substrates that contain an oxygen at the stereocenter. For example, BCL resolves β‐substituted‐γ‐acetyloxymethyl‐γ‐butyrolactones (acetates of a chiral primary alcohol) by hydrolysis of the acetate, but the enantioselectivity varies with the nature and orientation of the β‐alkyl substituent. BCL favors the (R)‐primary alcohol when the β‐alkyl substituent is hydrogen (E=30) or trans methyl (E=38), but the (S)‐primary alcohol when it is cis methyl (E=145). To rationalize this unusual selectivity, we used a combination of experiments to show the importance of polar interactions and modeling to reveal differences in orientations of the enantiomers. Removal of either the lactone carbonyl in the substrate or the polar side chains in the enzyme by using a related enzyme without these side chains decreased the enantioselectivity at least four‐fold. Modeling revealed that the slow enantiomers do not bind by exchanging the location of two substituents relative to the fast enantiomer. Instead, three substituents remain in the same region, but the fourth substituent, hydrogen, inverts to a new location, like an umbrella in a strong wind. In this orientation the favored stereoisomers have similar shapes, thus accounting for the unusual stereoselectivity. The ratio of catalytically productive orientations for the fast vs. slow enantiomers in a molecular dynamic simulation correlated (R2=0.82) with the degree of enantioselectivity including the case where the enantioselectivity reversed. Weighting this ratio by the ratio of H‐bonds in the polar interaction to account for different binding strengths improved the correlation with the measured enantioselectivity to R2=0.97. The modeling identifies key interactions responsible for high enantioselectivity in this class of substrates.magnified image

  DOI：

  10.1002/adsc.201400510