(4S,5R)-dihydro-5-hydroxymethyl-4-methyl-2(3H)-furanone | 73991-99-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (4S,5R)-dihydro-5-hydroxymethyl-4-methyl-2(3H)-furanone
• 英文别名: (4S,5R)-4-methyl-5-hydroxymethyltetrahydrofuran-2-one；(4S,5R)-5-(hydroxymethyl)-4-methyloxolan-2-one
• CAS: 73991-99-8
• 化学式: C₆H₁₀O₃
• 分子量: 130.144
• InChiKey: FBTOCHKZAQZWSO-WHFBIAKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4S,5R)-dihydro-5-hydroxymethyl-4-methyl-2(3H)-furanone 在 copper(l) iodide potassium carbonate 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 69.0h， 生成 (3S,4S)-4-ethyl-3-methyl-γ-butyrolactone
  参考文献：
  名称：

  Formal Synthesis of (-)-Serricornin

  摘要：

  A formal synthesis of sex pheromone (-)-serricornin was achieved via (4S,5S)-5-ethyl-4-methyltetrahydrofufan-2-one prepared from lipase PS-resolved (4S, 5R)-4-methyl-5-acetyloxymethyltetrahydrofuran-2-one.

  DOI：

  10.1080/00397910008087359
• 作为产物：
  描述：

  (4S,5S)-5-(iodomethyl)-4-methyldihydrofuran-2(3H)-one 在 palladium on activated charcoal 氢气 、 potassium benzyloxide 作用下， 生成 (4S,5R)-dihydro-5-hydroxymethyl-4-methyl-2(3H)-furanone
  参考文献：
  名称：

  Synthesis of the polyether antibiotic monensin. 2. Preparation of intermediates

  摘要：

  DOI：

  10.1021/ja00526a074

文献信息

• Stereoselective intramolecular bis-silylation of alkenes promoted by a palladium-isocyanide catalyst leading to polyol synthesis
  作者：Masahiro Murakami、Michinori Suginome、Kenzo Fujimoto、Hiroshi Nakamura、Pher G. Andersson、Yoshihiko Ito

  DOI：10.1021/ja00068a003

  日期：1993.7

  Stereoselective Intramolecular Bis-Silylation of Alkenes Promoted by a Palladium-Isocyanide Catalyst Leading to Polyol Synthesis

  钯-异氰化物催化剂促进烯烃的立体选择性分子内双-甲硅烷基化导致多元醇合成
• Regio-, stereo-, and enantioselective synthesis of cyclobutanols by means of the photoaddition of 1,3-dioxin-4-ones and lipase-catalyzed acetylation
  作者：Masayuki Sato、Hirohide Ohuchi、Yoshito Abe、Chikara Kaneko

  DOI：10.1016/s0957-4166(00)80211-6

  日期：1992.1

  Homochiral cis-2-hydroxymethylcyclobutanols, their all cis 3-methyl, and 4-hydroxymethyl derivatives were synthesized from 1,3-dioxin-4-ones via cyclobutane ring formation by [2+2]photocycloaddition, dioxanone ring cleavage, and reduction, followed by lipase-catalyzed kinetic resolution of the resulted cyclobutanols. The chiral cyclobutanols thus obtained have been converted to the corresponding gamma-lactones which are potential precursors for a series of biologically active compounds.
• Molecular Basis for the Enantio- and Diastereoselectivity of<i>Burkholderia cepacia</i>Lipase toward γ-Butyrolactone Primary Alcohols
  作者：Heesung Eum、Romas J. Kazlauskas、Hyun-Joon Ha

  DOI：10.1002/adsc.201400510

  日期：2014.11.24

  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
• Synthesis of the polyether antibiotic monensin. 2. Preparation of intermediates
  作者：David B. Collum、John H. McDonald、W. Clark Still

  DOI：10.1021/ja00526a074

  日期：1980.3
• Formal Synthesis of (-)-Serricornin
  作者：Hyun-Joon Ha、Yoon-Gil Yim

  DOI：10.1080/00397910008087359

  日期：2000.2

  A formal synthesis of sex pheromone (-)-serricornin was achieved via (4S,5S)-5-ethyl-4-methyltetrahydrofufan-2-one prepared from lipase PS-resolved (4S, 5R)-4-methyl-5-acetyloxymethyltetrahydrofuran-2-one.