Recent advances in radical-based C–F bond activation of polyfluoroarenes and gem-difluoroalkenes

Abstract

The direct employment of polyfluoroarenes and gem-difluoroalkenes as building blocks is regarded as one of the most effective and straightforward strategies for the introduction of fluorine-containing moieties into organic skeletons....

Recent Advances in C-F Bond Cleavage Enabled by Visible Light Photoredox Catalysis

“…Although there have been several reviews on C-F bond cleavage recently, each review has its specific focus, such as C-F bond activation by phosphorus compounds [25], or by metalloenzymes [26], C-F functionalization of trifluoromethyl groups [27,28], catalytic enantioselective functionalization of allylic C-F bond [29], transition metal-catalyzed C(sp 2 )-F cleavage [30], and deconstructive modes of halodifluoromethyl reagents [31]. This review focuses on the C-F bond cleavage enabled by visible light photoredox catalysis since 2018, classified by the types of fluorosubstrates [32,33].…”

Oxalates as Activating Groups for Tertiary Alcohols in Photoredox-Catalyzed gem-Difluoroallylation To Construct All-Carbon Quaternary Centers

“…The gem -difluoroalkenes are recognized as an important class of fluorinated compounds, which have wide application in agrochemistry, medicinal chemistry, and materials science. , For instance, the gem -difluoroalkene moiety is widely used as an ideal carbonyl group bioisostere in drug design and pharmaceuticals due to its high metabolic stability . They can also serve as versatile precursors toward valuable fluorine-containing molecules . Thus, substantial efforts have been made for their preparation, and two main strategies have been established: (1) gem -difluoromethylenation of carbonyl or diazo precursors , and (2) defluorinative alkylation, ,, that is, sequential introduction of an alkyl group into trifluoromethyl alkenes and β-fluorine-elimination.…”

“…Our method can also be conducted on a gram-scale with good yield (Scheme , 3a , 93%, 0.74 g). Functionalized gem -difluoroalkenes are versatile intermediates in synthetic chemistry . As shown in Scheme , further transformations of 3a proceeded smoothly, such as fluorohydroxylation ( 5 ) and hydrogenation ( 6 ), highlighting the potential utility of this protocol.…”

Visible-Light-Mediated α-Ketoacylations of NH-Sulfoximines with gem-Difluoroalkenes

“…gem -Difluoroalkenes 1 are synthetically flexible building blocks for the construction of a wide range of fluorine-containing or nonfluorinated molecules . Visible-light-induced cross-coupling reactions of gem -difluoroalkenes via radicals have attracted much attention, especially those resulting in defluorinative processes. Various approaches involving thiyl, carbon, and NHC-boryl radicals have been developed (Scheme (a)).…”