α-trifluoromethyl-δ-valerolactone

• 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: α-trifluoromethyl-δ-valerolactone
• 英文别名: 3-(trifluoromethyl)tetrahydro-2H-pyran-2-one；3-(Trifluoromethyl)oxan-2-one
• 化学式: C₆H₇F₃O₂
• 分子量: 168.116
• InChiKey: URLJJDQMVDMQRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2-三氟甲基环戊酮 在 三氟过氧乙酸 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 66.0h， 以78%的产率得到α-trifluoromethyl-δ-valerolactone
  参考文献：
  名称：

  Complete Reversal in Regioselectivity in the Baeyer−Villiger Reaction of an α-CF₃-Ketone and Theoretical Rationale for Axial Orientation of Sterically Demanding CF₃ Group at the Transition State

  摘要：

  [GRAPHICS]The regioselectivity of the Baeyer-Villiger reaction of alpha-CF3-ketone is completely reversed from that in alpha-F-eq-ketone. Theoretical study rationalized that the reaction proceeds with the sterically demanding CF3 group in an axial orientation by strong dipole interaction. The guiding principle that strong dipole interaction can overcome steric repulsion as a determining factor not only in regio- but also in stereocontrol is proposed.

  DOI：

  10.1021/ol0358298

文献信息

• Lewis Acid Catalyzed Synthesis of α-Trifluoromethyl Esters and Lactones by Electrophilic Trifluoromethylation
  作者：Dmitry Katayev、Václav Matoušek、Raffael Koller、Antonio Togni

  DOI：10.1021/acs.orglett.5b03088

  日期：2015.12.4

  An electrophilic trifluoromethylation of ketene silyl acetals (KSAs) by hypervalent iodine reagents 1 and 2 has been developed. The reaction proceeds under very mild conditions in the presence of a catalytic amount of trimethylsilyl bis(trifluoromethanesulfonyl)imide (up to 2.5 mol %) as a Lewis acid providing a direct access to a variety of secondary, tertiary, and quaternary α-trifluoromethyl esters

  已经开发了由高价碘试剂1和2进行的乙烯酮甲硅烷基缩醛（KSAs）的亲电子三氟甲基化反应。反应在非常温和的条件下，在催化量的三甲基甲硅烷基双（三氟甲磺酰基）酰亚胺（至多2.5 mol％）的路易斯酸存在下进行，可直接获得各种仲，叔和季α-三氟甲基酯和内酯，收率高（高达98％）。
• Photoredox Catalysis: A Mild, Operationally Simple Approach to the Synthesis of α-Trifluoromethyl Carbonyl Compounds
  作者：Phong V. Pham、David A. Nagib、David W. C. MacMillan

  DOI：10.1002/anie.201101861

  日期：2011.6.27

  A facile and efficient method for the α‐trifluoromethylation of carbonyl compounds and enolsilanes has been accomplished through application of a photoredox catalysis strategy. A one‐flask procedure for the direct α‐trifluoromethylation and α‐perfluoroalkylation of ketone, amide, and ester substrates as well as silylketene acetals is described (see scheme).

  通过应用光氧化还原催化策略，实现了一种简便有效的羰基化合物和烯醇硅烷的 α-三氟甲基化方法。描述了酮、酰胺和酯底物以及甲硅烷基烯酮缩醛的直接 α-三氟甲基化和 α-全氟烷基化的单烧瓶程序（参见方案）。