Olefin Scope. [a]1a (0.1 mmol), alkene (0.15 or 0.3 mmol), quinuclidine (0.2 mmol), [Ir(dF-CH3-ppy)2(dtbbpy)PF6] (2.0 mol%), DMF (0.2M), 34 W blue LED, ~ 40 °C, 16h. [b]Yield of isolated products. [c]dr was determined by 1H NMR of isolated product. [d]1.2 equiv. of 3-buten-2-one was used. [e]0.3 mmol scale. fEWG = electron withdrawing group; Ph = phenyl.