19031-70-0Relevant articles and documents
Transition metal-free cross-dehydrogenative arylation of unactivated benzylic C-H bonds
Spencer, Andrew R. A.,Grainger, Rachel,Panigrahi, Adyasha,Lepper, Thomas J.,Bentkowska, Katarzyna,Larrosa, Igor
, p. 14479 - 14482 (2020)
The cross-dehydrogenative arylation of benzylic C-H bonds with arenes provides straightforward access to synthetically useful 1,1-diarylmethanes, from readily available starting materials. Current approaches suffer from limited substrate scope, requirement for large excesses of alkyl arene and/or non-trivial reaction set up. We report a transition metal-free cross-dehydrogenative arylation of benzylic C-H bonds using alkyl benzene derivatives and electron-rich arenes as coupling partners. The method proceeds through the in situ generation of a reactive benzyl fluoride intermediate which then reacts with the nucleophilic arene. The reaction tolerates a wide variety of functional groups including unprotected polar functionality and has been applied to the late-stage benzylation of several biologically relevant molecules.
Light-Mediated Formal Radical Deoxyfluorination of Tertiary Alcohols through Selective Single-Electron Oxidation with TEDA2+.
Aguilar Troyano, Francisco José,Ballaschk, Frederic,Jaschinski, Marcel,?zkaya, Yasemin,Gómez-Suárez, Adrián
, p. 14054 - 14058 (2019/11/11)
The synthesis of tertiary alkyl fluorides through a formal radical deoxyfluorination process is described herein. This light-mediated, catalyst-free methodology is fast and broadly applicable allowing for the preparation of C?F bonds from (hetero)benzylic, propargylic, and non-activated tertiary alcohol derivatives. Preliminary mechanistic studies support that the key step of the reaction is the single-electron oxidation of cesium oxalates—which are readily available from the corresponding tertiary alcohols—with in situ generated TEDA2+. (TEDA: N-(chloromethyl)triethylenediamine), a radical cation derived from Selectfluor.
Fluorodecarboxylation, rearrangement and cyclisation: the influence of structure and environment on the reactions of carboxylic acids with xenon difluoride
Ramsden, Christopher A.,Shaw, Maxine M.
experimental part, p. 3321 - 3324 (2009/08/09)
The reactions of structurally diverse carboxylic acids with XeF2 in both CH2Cl2/Pyrex and CH2Cl2/PTFE have been studied. Pyrex appears to be a very effective heterogeneous catalyst for an electrophilic mode of reaction of polarised XeF2, leading to rearrangement, cyclisation and cationic products. In CH2Cl2/PTFE, fluorodecarboxylation is the main mode of reaction, in accordance with previous studies, and may occur via a SET reaction of unpolarised XeF2.