2-(1-butoxy)-6-methyl-2,3-dihydro-4H-pyran-4-one | 129665-17-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 2-(1-butoxy)-6-methyl-2,3-dihydro-4H-pyran-4-one
• 英文别名: 2-Butoxy-6-methyl-2,3-dihydropyran-4-one
• CAS: 129665-17-4
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: HAMQNLOAGKAYQE-UHFFFAOYSA-N

物化性质

• 沸点：
  254.4±29.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(1-butoxy)-6-methyl-2,3-dihydro-4H-pyran-4-one 在 sodium perborate 、 dimethyl sulfide borane 、 potassium tert-butylate 、 四丁基碘化铵 、 二异丁基氢化铝 、 二正丁基氧化锡 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 39.5h， 生成 n-Butyl 3,4-Anhydro-2,6-dideoxy-β-DL-ribo-hexopyranoside
  参考文献：
  名称：

  Acylketene [4+2] cycloadditions: divergent de novo synthesis of 2,6-dideoxy sugars

  摘要：

  The synthetic methodology demonstrated herein provides a divergent, de novo synthetic pathway to 2,6-dideoxy carbohydrates. Pyranone 2, which was prepared by [4 + 2] cycloaddition of the acylketene generated from dioxinone 1 with butyl vinyl ether, was converted in a straightforward manner to arabino-hexopyranosides olivoside 11 and oleandroside 12, and branched sugars olivomycoside 14 and chromoside B 15, with near complete control of relative stereochemistry at the three newly introduced stereogenic centers. Olivoside 11 proved to be a pivotal intermediate for elaboration to the ribo, lyxo, and xylo families of 2,6-dideoxy carbohydrates. Selective Mitsunobu inversion at C3 of 11 provided ready access to the ribo-pyranoside digitoxoside 17, whereas selective inversion at C4 of 11 or 12 via the intermediacy of the O4-trifluoromethanesulfonate ester gave rise to the lyxo-pyranosides olioside 23 and diginoside 21, respectively. A high-yielding sequence of reactions for the elaboration of 11 to lyxo-anhydro sugar 25 furnished an intermediate for the direct conversion to the xylo-pyranosides boivinoside 30 and sarmentoside 31 by a regioselective epoxide opening.

  DOI：

  10.1021/jo00054a022
• 作为产物：
  描述：

  乙烯基正丁醚 、 2,2,6-三甲基-4H-1,3-二英-4-酮 以 甲苯 为溶剂， 反应 2.5h， 以84%的产率得到2-(1-butoxy)-6-methyl-2,3-dihydro-4H-pyran-4-one
  参考文献：
  名称：

  酰基烯酮与烯醇醚的环加成反应：2-烷氧基-2,3-二氢-4h-吡喃-4-酮的一般合成。

  摘要：

  酰基烯酮的杂狄尔斯-阿尔德反应的详细描述4-6与富电子亲二烯体7-9为2-烷氧基-2,3-二氢-4H-吡喃-4-酮的简便合成10-12是提出了。

  DOI：

  10.1016/s0040-4039(00)97442-2

文献信息

• A convenient synthesis of unsymmetrical, substituted γ-pyrones from Meldrum's acid
  作者：Frank J. Zawacki、Michael T. Crimmins

  DOI：10.1016/0040-4039(96)01470-0

  日期：1996.9

  A unique approach to the synthesis of mono and disubstituted γ-pyrones from acylated Meldrum's acid and vinyl ethers has been developed. The convenient one pot synthesis of these versatile polyketide equivalents is accomplished without strong base or low temperatures.

  从酰化的麦德鲁姆酸和乙烯基醚合成单和双取代的γ-吡喃酮的独特方法已经开发出来。这些通用的聚酮化合物等效物的便捷一锅合成无需强碱或低温即可完成。
• An appraisal of oxoketene cycloaddition methodology for the synthesis of 2,6-dideoxysugars and fluorinated 2,6-dideoxysugars
  作者：Christophe Audouard、Kim Bettaney (née Middleton)、Châu T. Doan、Giuseppe Rinaudo、Peter J. Jervis、Jonathan M. Percy

  DOI：10.1039/b817672h

  日期：——

  The cycloaddition reaction of acylketenes with vinyl ethers affords an extremely direct route to 2,6-dideoxysugars and their methyl ethers. The lithium enolate of commercial 2,6,6-trimethyldioxinone 3 was fluorinated in good yield to afford fluorinated dioxinone 8. An illustrative range of fluorinated 2,6-dideoxysugar derivatives was prepared via the acetyl ketene–vinyl ether cycloadduct. Electronic

  酰基乙烯酮与乙烯基醚的环加成反应提供了一条直接的途径来制备2，6-二脱氧糖及其甲基醚。商业化的2,6,6-三甲基二恶英酮3的烯醇锂以良好的产率被氟化，得到氟化的二恶英酮8。通过乙酰基乙烯酮-乙烯基醚环加合物制备了一系列示例性的氟化2,6-二脱氧糖衍生物。进行电子结构计算以研究氟原子对（氟乙酰基）乙烯酮反应性中间体的易于形成和随后反应的影响。单个氟原子可降低约25％的片段化势垒。7.5 kJ摩尔-1，与实验结果一致，但对确定乙烯基醚添加速率或氧杂环丁烯二聚化的障碍几乎没有影响。
• Cycloaddition reactions of acyl ketenes with enol ethers: A general synthesis of 2-alkoxy-2,3-dihydro-4h-pyran-4-ones.
  作者：Robert S. Coleman、Eugene B. Grant

  DOI：10.1016/s0040-4039(00)97442-2

  日期：——

  A detailed description of the hetero Diels-Alder reactions of acyl ketenes 4-6 with electron-rich dienophiles 7-9 for the facile synthesis of 2-alkoxy-2,3-dihydro-4H-pyran-4-ones 10-12 is presented.

  酰基烯酮的杂狄尔斯-阿尔德反应的详细描述4-6与富电子亲二烯体7-9为2-烷氧基-2,3-二氢-4H-吡喃-4-酮的简便合成10-12是提出了。
• Acylketene [4+2] cycloadditions: divergent de novo synthesis of 2,6-dideoxy sugars
  作者：Robert S. Coleman、Janet R. Fraser

  DOI：10.1021/jo00054a022

  日期：1993.1

  The synthetic methodology demonstrated herein provides a divergent, de novo synthetic pathway to 2,6-dideoxy carbohydrates. Pyranone 2, which was prepared by [4 + 2] cycloaddition of the acylketene generated from dioxinone 1 with butyl vinyl ether, was converted in a straightforward manner to arabino-hexopyranosides olivoside 11 and oleandroside 12, and branched sugars olivomycoside 14 and chromoside B 15, with near complete control of relative stereochemistry at the three newly introduced stereogenic centers. Olivoside 11 proved to be a pivotal intermediate for elaboration to the ribo, lyxo, and xylo families of 2,6-dideoxy carbohydrates. Selective Mitsunobu inversion at C3 of 11 provided ready access to the ribo-pyranoside digitoxoside 17, whereas selective inversion at C4 of 11 or 12 via the intermediacy of the O4-trifluoromethanesulfonate ester gave rise to the lyxo-pyranosides olioside 23 and diginoside 21, respectively. A high-yielding sequence of reactions for the elaboration of 11 to lyxo-anhydro sugar 25 furnished an intermediate for the direct conversion to the xylo-pyranosides boivinoside 30 and sarmentoside 31 by a regioselective epoxide opening.