To Rollover or Not? Stereoelectronically Guided C-H Functionalization Pathways from Rhodium-Abnormal NHC Intermediates

Rollover C-H activation with transition-metal complexes has been found to be a difficult but viable pathway to functionalize potentially chelating molecules, which are otherwise reluctant to react further. However, selective rollover or nonrollover C-H activation pathway depends on the stereoelectronic demand of the associated organometallic intermediate(s). The presented work addresses the above issue on abnormal N-heterocyclic carbene (NHC) platform. Catalytic reactions of pyridine-imidazolium substrates with internal alkynes have been selectively guided toward either rollover or nonrollover C-H functionalization route via fulfilling the steric and electronic demands of the relevant rhodium(III)-abnormal NHC metallacyclic intermediates.