4-(5-methyl-2-furyl)pentan-4-olide

• 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: 4-(5-methyl-2-furyl)pentan-4-olide
• 英文别名: 5-Methyl-5-(5-methylfuran-2-yl)oxolan-2-one；5-methyl-5-(5-methylfuran-2-yl)oxolan-2-one
• 化学式: C₁₀H₁₂O₃
• 分子量: 180.203
• InChiKey: ZQHMVQITCFVJFA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  39.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-(5-methylfuran-2-yl)pent-4-yn-2-ol 在 (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride N-羟基丁二酰亚胺 、 三(2-呋喃基)膦 、 四丁基溴化铵 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以51%的产率得到4-(5-methyl-2-furyl)pentan-4-olide
  参考文献：
  名称：

  Ruthenium-Catalyzed Cycloisomerization−Oxidation of Homopropargyl Alcohols. A New Access to γ-Butyrolactones

  摘要：

  Vinylidenemetal species, which readily form from terminal alkynes under mild conditions, have rarely been utilized as reactive intermediates in a catalytic cycle. The conversion of homopropargyl alcohols via such intermediates to metal-complexed oxacarbenes led to the development of an "oxidant" compatible with a ruthenium complex capable of performing the cycloisomerization, that would convert them to lactones. None of the oxidants known to stoichiometrically convert isolated metallooxacarbenes to esters are effective. The unconventional "oxidants", N-hydroxyimides, proved to be capable of effecting the desired transformation, with N-hydroxysuccinimide being the "oxidant" of choice. The procedure of choice employs cyclopentadienyl (1,4-cyclooctadiene) ruthenium chloride and trifuryl phosphine as the precatalyst in the presence of tetra-n-butylammonium bromide or hexafluorophosphate with N-hydroxysuccinimide as the oxidant in DMF-water at 95 degrees. In this way, a wide diversity of homopropargyl alcohols were converted to gamma-butyrolactones with excellent chemoselectivity. Lactones synthesized include an intermediate toward a platelet aggregation inhibitor, a fruit flavor principle, an inhibitor of binding of phorbol esters to PKC-alpha, a tobacco constituent, a wood constituent (quercus lactone), an aldosterone antagonist (spironolactone) precursor, and an acetogenin known for pesticidal and antitumor activities (muricatacin).

  DOI：

  10.1021/ja992013m

文献信息

• New lactones from tobacco
  作者：Tore. Pettersson、Ann Marie. Eklund、Inger. Wahlberg

  DOI：10.1021/jf00035a052

  日期：1993.11

  Thirteen lactones (1-13) have been isolated from an extract of sun-cured leaves of Greek tobacco by using HPLC methods. All but four of these (1-9) are new natural products. They have been identified as 3-(4-methyl-1-pentyl)-2-buten-4-olide (1), 3-isopropyl-2-penten-4-olide (2),3-ethyl-4-methyl-2-penten-4-olide (3), 4-methyl-3-(3-oxo-1-butyl)-2-penten-4-olide (4), 3-methyl-7-oxo-2-octen-4-olide (5), 4-(5-methyl-2-furyl)pentan-4-olide (6), (3R*,4R*,7R*)-3,7-epoxy-4,8-dimethyl-8-nonen-4-olide (7), 3-isopropyl-2,4-pentadien-5-olide (8), and (1S,7R)-4-oxa-7,11,11-trimethylbicyclo[5.4.0]undecan-3-one (9) by spectral methods, 2D NMR being a helpful tool. The syntheses of two of the lactones (1 and 9) are reported, and the plausible biogenesis of the new lactones is discussed. (Z)-6-Nonen-4-olide (10) and 5-methyl-4-hexanolide (11), now also isolated, are new to tobacco, while two 3-methyl-4-pentanolides (12 and 13), previously known as tobacco constituents, have now been identified as the 3R,4R- and 3R,4S-isomers by comparison of their optical rotations and spectral data with those of corresponding synthetic samples.
• Ruthenium-Catalyzed Cycloisomerization−Oxidation of Homopropargyl Alcohols. A New Access to γ-Butyrolactones
  作者：Barry M. Trost、Young H. Rhee

  DOI：10.1021/ja992013m

  日期：1999.12.1

  Vinylidenemetal species, which readily form from terminal alkynes under mild conditions, have rarely been utilized as reactive intermediates in a catalytic cycle. The conversion of homopropargyl alcohols via such intermediates to metal-complexed oxacarbenes led to the development of an "oxidant" compatible with a ruthenium complex capable of performing the cycloisomerization, that would convert them to lactones. None of the oxidants known to stoichiometrically convert isolated metallooxacarbenes to esters are effective. The unconventional "oxidants", N-hydroxyimides, proved to be capable of effecting the desired transformation, with N-hydroxysuccinimide being the "oxidant" of choice. The procedure of choice employs cyclopentadienyl (1,4-cyclooctadiene) ruthenium chloride and trifuryl phosphine as the precatalyst in the presence of tetra-n-butylammonium bromide or hexafluorophosphate with N-hydroxysuccinimide as the oxidant in DMF-water at 95 degrees. In this way, a wide diversity of homopropargyl alcohols were converted to gamma-butyrolactones with excellent chemoselectivity. Lactones synthesized include an intermediate toward a platelet aggregation inhibitor, a fruit flavor principle, an inhibitor of binding of phorbol esters to PKC-alpha, a tobacco constituent, a wood constituent (quercus lactone), an aldosterone antagonist (spironolactone) precursor, and an acetogenin known for pesticidal and antitumor activities (muricatacin).