Iron-catalysed alkene and heteroarene H/D exchange by reversible protonation of iron-hydride intermediates

Abstract

C-H functionalisation reactions offer a sustainable method for molecular construction and diversification. These reactions however remain dominated by precious metal catalysis. While significant interest in iron-catalysed C-H activation reactions has...

Late-Stage C–H Deuteration of Organic Compounds via Ligand-Enabled Palladium-Catalyzed Hydrogen Isotope Exchange

“…A drawback of our method for the deuteration of arenes remained that it was not generally applicable to heteroarenes, giving low degrees of deuterium incorporation or leading to substrate decomposition. 31 Methods for nondirected deuteration of heteroarenes have been reported using Fe, 10c 28 30 32 Ni, 29,33 Ag, 34 Ru 35 and other catalytically active metals, 9 and typically induce a site-specific deuteration at inherently more reactive positions. Additionally, these methods are specifically optimized for particular classes of heteroarenes.…”

Modern Organometallic C−H Functionalizations with Earth‐Abundant Iron Catalysts: An Update

“…[76] This concept was recently exploited by Thomas and co-workers who reported a protocol for the iron-catalyzed HIE which was accomplished using CD 3 OD as the deuterium source, under photoirradiation with blue light (Scheme 29). [77] The key features of this novel protocol include the use of the readily available, bench-stable [dmpe 2 FeCl 2 ] as the pre-catalyst, the isolation and characterization of key CÀ H metalation intermediates and the unprecedented H/D exchange reaction of alkene CÀ H bonds. The substrate scope included a wide range of sensitive functional groups and heterocycles that reacted smoothly to give the deuterated products in good yields (Scheme 29, a).…”

Iron‐Catalysed C(sp2)‐H Borylation with Expanded Functional Group Tolerance†

“…This could be achieved through the addition of an exogenous nucleophile which in combination with HBpin, would form an organometallic hydride donor in an operationally simple manner (Scheme 1c). [ 18,34 ] This complex and the analogous manganese species have shown good activity for C(sp 2 )‐H borylation under blue light irradiation, but these systems were limited to the borylation of heteroarenes. [ 17 ] Additionally, free alcohols and amines would be tolerated by use of HBpin as a traceless protecting group.…”