1,6-Dioxaspiro<4.5>dec-9-ene | 119529-03-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,6-Dioxaspiro<4.5>dec-9-ene
• 英文别名: 1,7-Dioxaspiro<5.4>dec-4-ene；1,6-dioxa-spiro[4.5]dec-9-ene；1,6-Dioxaspiro[4.5]dec-9-ene
• CAS: 119529-03-2
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: NVJUEJIIKVSYME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,6-Dioxaspiro<4.5>dec-9-ene 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 1,6-Dioxaspiro<4.5>decan-9-ol 、 1,6-Dioxaspiro<4.5>decan-9-ol
  参考文献：
  名称：

  .alpha.-Bromo spiroketals: stereochemistry and elimination reactions

  摘要：

  The simple spiroketals, 1,6-dioxaspiro[4.4]nonane (2), 1,6-dioxaspiro[4.5]decane (5), 1,7-dioxaspiro[5.5]undecane (6), and (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (7), have been brominated by bromine in carbon tetrachloride/calcium carbonate or acetic acid, and a number of mono-, di-, and tribromo derivatives have been characterized. The relative stereochemistries have been established by correlated H-1 and C-13 NMR spectroscopy and X-ray crystal structure determinations. Dehydrobromination with potassium tert-butoxide in either dimethyl sulfoxide or tetrahydrofuran is facile for the axial monobromides, although both axial and equatorial bromides derived from 1,6-dioxaspiro[4.5]decane (5) and 1,7-dioxaspiro[5.5]undecane (6) dehydrobrominate to provide 1,6-dioxaspiro[4.5]dec-9-ene (35) and 1,7-dioxaspiro[5.5]undec-4-ene (26), respectively. Hydration of these readily acquired alkenes furnishes the corresponding 9- and 4-ols, respectively, with the latter being components of the rectal glandular secretion of Bactrocera oleae (olive fly), Bactrocera cacuminatus, and Bactrocera distincta. These studies indicate that alpha-bromination of suitable spiroketals may be a viable later step in the synthesis of alpha-bromine-containing spiroketal metabolites such as obtusin and neoobtusin.

  DOI：

  10.1021/jo00061a025
• 作为产物：
  描述：

  1-(tert-butyldimethylsilyloxy)-4-pentyne 在 正丁基锂 、 四丁基氟化铵 、 mercuric triflate 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 5.83h， 生成 1,6-Dioxaspiro<4.5>dec-9-ene
  参考文献：
  名称：

  A Highly Efficient Access to Spiroketals, Mono-unsaturated Spiroketals, and Furans: Hg(II)-Catalyzed Cyclization of Alkyne Diols and Triols

  摘要：

  Hg(II) salts are identified as highly efficient catalysts for the versatile construction of spiroketals from alkyne diols in aqueous conditions. Monounsaturated spiroketals and furans were accessed with equal ease when propargylic triols (or propargylic diols) were subjected to similar conditions. Even the semiprotected alkyne diols gave the corresponding spiroketals with the same ease in a cascade manner. The reactions are Instant and high yielding at ambient temperatures. Regioselectivity issues are well addressed.

  DOI：

  10.1021/ol201102x

文献信息

• Gold(I)-, Palladium(II)-, Platinum(II)-, and Mercury(II)-Catalysed Spirocyclization of 1,3-Enynediols: Reaction Scope
  作者：Alexander Zhdanko、Martin E. Maier

  DOI：10.1002/ejoc.201402029

  日期：2014.6

  spirocyclization of different 1,3-enynediols was investigated. The reaction was only efficient for the synthesis of [5,6]-spiroacetals. In this case, the reaction was characterized by almost quantitative yields, short reaction times, and low catalyst loadings (0.5–1 %). When the synthesis of [6,6]-spiroacetals was attempted, the reaction suffered from poor regioselectivity and a higher propensity of the

  研究了不同 1,3-烯炔二醇的螺环化。该反应仅对[5,6]-螺缩醛的合成有效。在这种情况下，该反应的特点是收率几乎是定量的、反应时间短和催化剂负载量低（0.5-1%）。当尝试合成 [6,6]-螺缩醛时，该反应的区域选择性较差，中间体二烯醇醚在酸性条件下更容易分解，因此不再可行。但是可以在较温和的条件下以区域异构体的混合物形式干净地生成二烯醇醚。这种反应效率的显着差异是由于不稳定的二烯醇醚环化得更快，得到 [5,6]-螺缩醛而不是得到 [6,6]-螺缩醛。在这项研究中，
• A stereoselective synthesis of functionalized alkenyllithiums and alkenyl cyanocuprates by the copper(I)-catalyzed coupling of organolithium reagents with .alpha.-lithiated cyclic enol ethers
  作者：Philip Kocienski、Sjoerd Wadman、Kelvin Cooper

  DOI：10.1021/ja00188a095

  日期：1989.3
• A Highly Efficient Access to Spiroketals, Mono-unsaturated Spiroketals, and Furans: Hg(II)-Catalyzed Cyclization of Alkyne Diols and Triols
  作者：Kontham Ravindar、Maddi Sridhar Reddy、Pierre Deslongchamps

  DOI：10.1021/ol201102x

  日期：2011.6.17

  Hg(II) salts are identified as highly efficient catalysts for the versatile construction of spiroketals from alkyne diols in aqueous conditions. Monounsaturated spiroketals and furans were accessed with equal ease when propargylic triols (or propargylic diols) were subjected to similar conditions. Even the semiprotected alkyne diols gave the corresponding spiroketals with the same ease in a cascade manner. The reactions are Instant and high yielding at ambient temperatures. Regioselectivity issues are well addressed.
• .alpha.-Bromo spiroketals: stereochemistry and elimination reactions
  作者：Elvie N. Lawson、William Kitching、Colin H. L. Kennard、Karl A. Byriel

  DOI：10.1021/jo00061a025

  日期：1993.4

  The simple spiroketals, 1,6-dioxaspiro[4.4]nonane (2), 1,6-dioxaspiro[4.5]decane (5), 1,7-dioxaspiro[5.5]undecane (6), and (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (7), have been brominated by bromine in carbon tetrachloride/calcium carbonate or acetic acid, and a number of mono-, di-, and tribromo derivatives have been characterized. The relative stereochemistries have been established by correlated H-1 and C-13 NMR spectroscopy and X-ray crystal structure determinations. Dehydrobromination with potassium tert-butoxide in either dimethyl sulfoxide or tetrahydrofuran is facile for the axial monobromides, although both axial and equatorial bromides derived from 1,6-dioxaspiro[4.5]decane (5) and 1,7-dioxaspiro[5.5]undecane (6) dehydrobrominate to provide 1,6-dioxaspiro[4.5]dec-9-ene (35) and 1,7-dioxaspiro[5.5]undec-4-ene (26), respectively. Hydration of these readily acquired alkenes furnishes the corresponding 9- and 4-ols, respectively, with the latter being components of the rectal glandular secretion of Bactrocera oleae (olive fly), Bactrocera cacuminatus, and Bactrocera distincta. These studies indicate that alpha-bromination of suitable spiroketals may be a viable later step in the synthesis of alpha-bromine-containing spiroketal metabolites such as obtusin and neoobtusin.