82027-45-0Relevant articles and documents
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
supporting information, p. 5562 - 5566 (2020/03/04)
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).
Effect of α-carbomethoxy group on the reactivity of benzyl cations in solution
Schepp, Norman P.,Wirz, Jakob
, p. 11749 - 11753 (2007/10/02)
Substituted α-carbomethoxybenzyl cations have been generated upon 248- or 308-nm laser flash photolysis of appropriately substituted methyl phenyldiazoacetates in aqueous solution, 2,2,2-trifluoroethanol (TFE), or 1,1,1,3,3,3-hexafluoroisopropyl alcohol (
