We have developed the first example of a photoredox catalytic method for the formation of carbon-fluorine (C-F) bonds. The mechanism has been studied using transient absorption spectroscopy and involves a key single-electron transfer from the (3)MLCT (triplet metal-to-ligand charge transfer) state of Ru(bpy)3(2+) to Selectfluor. Not only does this represent a new reaction for photoredox catalysis, but the mild reaction conditions and use of visible light also make it a practical improvement over previously developed UV-mediated decarboxylative fluorinations.

Monofluoroalkenes have found wide application in organic chemistry, medicinal chemistry, and materials science. This review summarizes the most recent advances made regarding the preparation of monofluoroalkenes, covering the period between October 2010 and September 2017. This review is divided in three main parts, one for each possible substitution pattern, namely di-, tri-, and tetrasubstituted. Then, for each class, further subclassification is made according to the reaction type.1 Introduction2 Disubstituted Monofluoroalkenes2.1 Disubstituted α-Monofluoroalkenes2.2 Disubstituted β-Monofluoroalkenes3 Trisubstituted Monofluoroalkenes4 Tetrasubstituted Monofluoroalkenes5 Conclusions

Monofluoroalkenes are fluorinated motifs that can be used to replace amide bonds. In order to be incorporated into peptides, it is normally necessary to first synthesize a dipeptide where the amide bond has been replaced with a monofluoroalkene. In that context, this review will present the racemic and enantioselective synthesis of monofluoroalkene-based dipeptide isosteres described since 2007. Some applications of those compounds will also be presented.

Solid-state 19 FNMR is ap owerful methodt o study the interactions of biologically active peptides with membranes. So far,i nl abelled peptides, the 19 F-reporter group has alwaysb een installed on the side chain of an amino acid. Given the fact that monofluoroalkenes are non-hydrolyzable peptideb ond mimics, we have synthesized am onofluoroalkene-based dipeptide isostere, Val-Y[(Z)-CF=CH]-Gly,a nd insertedi ti nt he sequence of two well-studied antimicrobial peptides:P GLa and (KIGAKI) 3 are representatives of an a-helix and a b-sheet. The conformations and biological activities of these labeled peptides were studied to assess the suitability of monofluoroalkenes for 19 FNMR structure analysis.[a] M.