Photoredox‐gesteuerte Mono‐ und Di‐Multifluorarylierung von C(sp³)‐H‐Bindungen mit Arylfluoriden

Abstract

Die kontrollierbare Mono-und Di-Multifluorarylierung von acyclischen und cyclischen N-Arylaminen mit Arylfluoriden über photokatalysierte duale C(sp 3

Photocatalytic C−F Bond Activation of Fluoroarenes, gem‐Difluoroalkenes and Trifluoromethylarenes

“…SCE in THF, [32] E(Ir III /Ir II )=−1.32 V vs . SCE in MeCN), a different mechanism from Hashmi's proposal [26] was proposed, not involving the formation of the polyfluoroaryl radical. First, the carboxylic acids 17 were reduced by the excited Ir(III)* complex ((E red (*Ir III /Ir II )=−1.48 V vs .…”

“…via carbon–carbon radical coupling process in 2017 (Scheme 9). [26] The controllable mono‐ and di‐multifluoroarylation of aryl‐dialkyl tertiary amines with polyfluoroarenes was developed by photocatalytic dual C(sp 3 )−H/C(sp 2 )−F functionalizations with [Ir(dtbbpy)(ppy) 2 ]PF 6 as the PC and NaOAc or NaHCO 3 as the bases, which provided new methodologies to deliver various valuable α‐fluoroarylated amines. The di‐multifluoroarylation could be achieved via directly adding another polyfluoroarene substrate into the solution of the in‐situ formed mono‐multifluoroarylation products.…”

“…Another type of defluoroalkylation was reported by Xie and Hashmi et al via carbon-carbon radical coupling process in 2017 (Scheme 9). [26] The controllable mono-and di-multifluor- ). [27] A reductive quenching catalytic cycle involving photooxidation of t-BuO À , reduction of fluoroarene substrates, 1,5-hydrogen atom transfer (HAT), cyclization and final HAT process was proposed.…”

Advances in the Synthesis of Imine‐Containing Azaarene Derivatives via Photoredox Catalysis

“…In 2017, Xie, Hashmi and co‐workers reported a controllable mono‐ and di‐polyfluoroarylation of cyclic and acyclic N ‐aryl amines 99 with aryl fluorides by a photoredox‐catalysed dual C(sp 3 )−H/C(sp 2 )−F functionalization (entry 3, Scheme A) . Pentafluoropyridines 102 were used as the reaction partners of tertiary amines.…”

Transition‐Metal‐Free Reductive Functionalization of Tertiary Carboxamides and Lactams for α‐Branched Amine Synthesis

“…[2] Recently, the a-CÀH arylation/alkylation of amines by photoredox catalysis has enabled the synthesis of such constructs under much milder reaction conditions. [3] Another promising approach to access a-branched amines is reductive functionalization of readily available and benchstable carboxamides. [4,5] In this context, several methods have been developed by taking advantage of electrophilic activation or controlled hydride reduction (including transitionmetal-catalyzed hydrosilylation) as the initiation process to enable subsequent selective functionalization whilst minimizing over-reduction.…”