Organometallic reagents are routinely used as fundamental building blocks in organic chemistry to rapidly diversify molecular fragments via carbanion intermediates.1 However, the catalytic generation of carbanion equivalents, particularly from sp3-hybridised alkyl scaffolds, remains an underdeveloped goal in chemical synthesis. Alkenes constitute an attractive source of latent alkyl carbanion equivalents, however, methods for the conversion of carbon-carbon π‑bonds into carbanions is challenged by the need for aggressive stoichiometric reductants.2 Here we disclose an approach for the controlled generation of 2-electron carbon nucleophiles via single electron reduction of aryl alkenes, facilitated by the highly reducing environment of multiphoton photoredox catalysts.3 We demonstrate that alkene radical anions engage in catalytic, metal free, intermolecular C-C bond-forming reactions with carbonyl derivatives. Under this reaction manifold, the alkene can be considered a dicarbanion synthon offering new opportunities for orthogonal diversification. This concept was illustrated by the development of four distinct C-C bond forming reactions with aromatic alkenes: hydroalkoxylation, hydroamidation, aminoalkylation and carboxyaminoalkylation, to generate a range of valuable and complex scaffolds.4,5