Photoinduced Proton-Transfer Reactions for Mild O-H Functionalization of Unreactive Alcohols.

ABSTRACT: 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

SUBMITTER: Jana S 

PROVIDER: S-EPMC7154649 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature