Here we report the surprising discovery that high-energy vinyl carbocations can be generated under strongly basic conditions, and that they engage in intramolecular sp3 C–H insertion reactions through the catalysis of weakly coordinating anion salts. This approach relies on the unconventional combination of lithium hexamethyldisilazide base and the commercially available catalyst, triphenylmethylium tetrakis(pentafluorophenyl)-borate. These reagents form a catalytically active lithium species that enables the application of vinyl cation C–H insertion reactions to heteroatom-containing substrates.

Herein we report the 3,5bistrifluoromethylphenyl urea-catalyzed functionalization of unactivated C-H bonds. In this system, the urea catalyst mediates the formation of high-energy vinyl carbocations that undergo facile C-H insertion and Friedel-Crafts reactions. We introduce a new paradigm for these privileged scaffolds where the combination of hydrogen bonding motifs and strong bases affords highly active Lewis acid catalysts capable of ionizing strong C-O bonds. Despite the highly Lewis acidic nature of these catalysts that enables triflate abstraction from sp 2 carbons, these newly found reaction conditions allow for the formation of heterocycles and tolerate highly Lewis basic heteroaromatic substrates. This strategy showcases the potential utility of dicoordinated vinyl carbocations in organic synthesis.

From the preparation of pharmaceuticals to enzymatic construction of natural products, carbocations are central to molecular synthesis. Although these reactive intermediates are engaged in stereoselective processes in nature, exerting enantiocontrol over carbocations with synthetic catalysts remains challenging. Many resonance-stabilized tricoordinated carbocations, such as iminium and oxocarbenium ions, have been applied in catalytic enantioselective reactions. However, their dicoordinated counterparts (aryl and vinyl carbocations) have not, despite their emerging utility in chemical synthesis. We report the discovery of a highly enantioselective vinyl carbocation carbon–hydrogen (C–H) insertion reaction enabled by imidodiphosphorimidate organocatalysts. Active site confinement featured in this catalyst class not only enables effective enantiocontrol but also expands the scope of vinyl cation C–H insertion chemistry, which broadens the utility of this transition metal–free C(sp 3 )–H functionalization platform.

The relative Lewis acidity of a variety of metal−ligand catalyst complexes is quantified using 31 P NMR spectroscopy. Three 31 P NMR probes, including two new bidentate binding probes, are compared on the basis of different binding modes (i.e., monodentate vs bidentate) and the relative scale of their downfield shift upon binding to Lewis acid complexes. Bidentate coordination of catalyst complexes including metal catalysts, ligands, and counterions were assessed due to their importance to asymmetric catalysis. The effect of ligands, counterions, and additives on Lewis acidity is quantified and correlated to reaction yield at an early time point as an approximation for catalytic activity/efficiency and chelation mode in two organic transformations. Binding studies were performed under catalytically relevant conditions, giving further applicability to synthesis. Insight into activation modes are revealed through this analysis.

The electrochemical generation of vinyl carbocations from alkenyl boronic esters and boronates is reported. Using easy-tohandle nucleophilic fluoride reagents, these intermediates are trapped to form fully substituted vinyl fluorides. Mechanistic studies support the formation of dicoordinated carbocations through sequential single-electron oxidation events. Notably, this electrochemical fluorination features fast reaction times and Lewis acid-free conditions. This transformation provides a complementary method to access vinyl fluorides with simple fluoride salts such as TBAF.