Reaction discovery and optimisation. To determine whether the nucleophilicity and electrophilicity of free radicals could be regulated and utilised for the efficient synthesis of various compounds from the same precursor, we studied the intramolecular Michael addition and anti-Michael addition reactions of methyl (E)-3-(2-(((E)-benzylidene)amino)phenyl)acrylate (2). In our previous work, we had reported that an imine C-H bond can be photoactivated to generate a carbon radical . Theoretically, if the nucleophilicity and electrophilicity of free radicals could be regulated by altering the reaction conditions, the resulting carbon radical could be programmed to attack either the α or β position in 2 to form methyl 2-phenylquinoline-3-carboxylate (3a) or methyl 2-(2-phenyl-3H-indol-3-ylidene)acetate (4a), respectively. To evaluate this hypothesis, various reaction conditions were investigated and indeed, the synthesis of 3a was successfully achieved. However, even after numerous attempts, 4a could not be synthesised. Further investigations suggested that 4a rearranged to form methyl 3-phenylquinoline-4carboxylate (5a), as shown in Scheme 1. Based on these observations, the reaction conditions were subsequently optimised to regulate the nucleophilicity and electrophilicity of the imine carbon radical to improve the yield of both 3a and 5a entities.