32191-63-2Relevant academic research and scientific papers
Photoinduced Proton-Transfer Reactions for Mild O-H Functionalization of Unreactive Alcohols
Empel, Claire,Ho, Junming,Jana, Sripati,Koenigs, Rene M.,Li, Fang,Yang, Zhen
, p. 5562 - 5566 (2020)
Hexafluoroisopropanol is typically considered as an unreactive solvent and not as a reagent in organic synthesis. Herein, we report on a mild and efficient photochemical reaction of aryl diazoacetates with hexafluoroisopropanol that enables, under stoichiometric reaction conditions, the synthesis of fluorinated ethers in excellent yield. Mechanistic studies indicate there is a preorganization of hexafluoroisopropanol and the diazoalkane acts as an unreactive hydrogen-bonding complex. Only after photoexcitation does this complex undergo a protonation-substitution reaction to the reaction product. Investigations on the applicability of this photochemical transformation show that a broad variety of acidic alcohols can be subjected to this transformation and thus demonstrate the feasibility of this concept for O-H functionalization reactions (54 examples, up to 98 % yield).
