The stereodivergent iridium-catalyzed allylic alkylation and fluorination of acyclic ketones is described. a-Pyridyl-a-fluoroketones with vicinal tertiary and quaternary stereocenters were obtained in moderate to excellent yields and stereoselectivities.D istinct from knowns tereodivergent synthesis,f or whicht wo different chiral catalysts are required in general, herein we report as equence-dependent stereodivergent synthesis.W itho nly as ingle chiral Ir catalyst, all four possible stereoisomers of the products were prepared from the same starting materials by simply adjusting the sequence of asymmetric allylic alkylation and fluorination and varying the absolute configuration of the Ir catalyst.