cis-2-ethynylcycloheptanol | 25127-83-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-2-ethynylcycloheptanol
• 英文别名: cis-2-Ethinylcycloheptanol；(1S,2S)-2-ethynylcycloheptan-1-ol
• CAS: 25127-83-7；61967-62-2；79894-69-2
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: XHVALGTUZARLIW-BDAKNGLRSA-N

物化性质

• 沸点：
  72 °C(Press: 3.5 Torr)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-2-ethynylcycloheptanol 在 (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride N-羟基丁二酰亚胺 、 三(2-呋喃基)膦 、 tert-butylammonium hexafluorophosphate(V) 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以72%的产率得到cis-octahydro-2H-cycloheptafuran-2-one
  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
• 作为产物：
  描述：

  (1R,2S)-2-乙炔基环庚烷-1-醇 在 sodium dichromate 、 硫酸 、 L-Selectride 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 生成 cis-2-ethynylcycloheptanol
  参考文献：
  名称：

  Palladium-catalyzed cyclocarbonylation of acetylenic alcohols to methylene lactones. Scope and synthesis of appropriate substrates

  摘要：

  DOI：

  10.1021/ja00415a020

文献信息

• Hanack, Michael; Schuhmacher, Werner; Kunzmann, Erich, Chemische Berichte, 1982, vol. 115, # 4, p. 1467 - 1487
  作者：Hanack, Michael、Schuhmacher, Werner、Kunzmann, Erich

  DOI：——

  日期：——
• Palladium-catalyzed cyclocarbonylation of acetylenic alcohols to methylene lactones. Scope and synthesis of appropriate substrates
  作者：Timothy F. Murray、Edward G. Samsel、Vijaya Varma、Jack R. Norton

  DOI：10.1021/ja00415a020

  日期：1981.12
• 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).