3-benzyloxy-4,4-difluoro-deca-1,9-dien-5-one | 930286-11-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-benzyloxy-4,4-difluoro-deca-1,9-dien-5-one
• 英文别名: 3-(Benzyloxy)-4,4-difluoro-1,9-decadiene-5-one；4,4-difluoro-3-phenylmethoxydeca-1,9-dien-5-one
• CAS: 930286-11-6
• 化学式: C₁₇H₂₀F₂O₂
• 分子量: 294.341
• InChiKey: LWQZJYHRXLGKDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-benzyloxy-4,4-difluoro-deca-1,9-dien-5-one 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 Neolyst titanium(IV) isopropylate 、 ruthenium trichloride 、 sodium periodate 、 cerium(III) chloride 、 15-冠醚-5 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 反应 90.0h， 生成 3RS-benzyloxy-1RS,4RS-bis(dibenzylphosphoryloxy)-2,2-difluoro-9-oxa-1RS,5SR-bicyclo[3.3.1]nonane
  参考文献：
  名称：

  Total Syntheses of Conformationally Locked Difluorinated Pentopyranose Analogues and a Pentopyranosyl Phosphate Mimetic

  摘要：

  Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a glycosyl phosphate.

  DOI：

  10.1021/jo0620258
• 作为产物：
  描述：

  4-戊烯醛 在 甲醇 、 4-二甲氨基吡啶 、 sodium hydroxide 、 氯化亚砜 、 poly(vinylpyridine) 、 四丁基硫酸氢铵 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 39.5h， 生成 3-benzyloxy-4,4-difluoro-deca-1,9-dien-5-one
  参考文献：
  名称：

  Total Syntheses of Conformationally Locked Difluorinated Pentopyranose Analogues and a Pentopyranosyl Phosphate Mimetic

  摘要：

  Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a glycosyl phosphate.

  DOI：

  10.1021/jo0620258

文献信息

• Selected Substituent Effects on the Rate and Efficiency of Formation of an Eight-Membered Ring by RCM
  作者：Lisa Mitchell、John A. Parkinson、Jonathan M. Percy、Kuldip Singh

  DOI：10.1021/jo702726b

  日期：2008.3.1

  highlight a discrepancy between cyclization rate and cyclization efficiency. Cyclization rates change modestly as the oxygen function at the allylic position is varied, and increase upon gem-dimethylation. Cyclization efficiency has also been quantified for four substrates, revealing a range of effective molarities (EMs) of 2 orders of magnitude that are substituent dependent. The most efficient cyclization

  对形成环辛烯酮的一系列反应的研究突显了环化速率和环化效率之间的差异。随着烯丙基位置氧功能的变化，环化速率适度变化，随着宝石的增加，环化速率增加-二甲基化。还已经对四种底物的环化效率进行了定量，揭示了取决于取代基的2个数量级的有效摩尔浓度（EMs）范围。最有效的环化作用似乎是由于抑制了低聚反应开始的交叉复分解途径，而不是由特别快速的环化反应引起的。在Ti（IV）助催化剂存在下，二烯单体平稳地转变为八元环产物，而没有二聚体或其他低聚物的介入，这表明环化是动力学而非热力学控制的。在宝石二烷基效果也证明是动能。
• Total Syntheses of Conformationally Locked Difluorinated Pentopyranose Analogues and a Pentopyranosyl Phosphate Mimetic
  作者：Jonathan A. L. Miles、Lisa Mitchell、Jonathan M. Percy、Kuldip Singh、E. Uneyama

  DOI：10.1021/jo0620258

  日期：2007.3.1

  Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a glycosyl phosphate.