The ability to directly transform unfunctionalized precursors into complex molecules is an important goal of synthetic organic chemistry.  As one of the major challenges in this area, the activation of carbon-hydrogen bonds has recently become increasingly important as a versatile method of forming carbon-carbon bonds.  In contrast to the numerous examples of aromatic C-H bond alkylation, the alkylation of olefinic C-H bonds remains limited in the scope.  We report the stereoselective β-alkylation of α,β-unsaturated aldimines via C-H activation followed by imine hydrolysis to provide tri- and tetrasubstituted α,β-unsaturated aldehydes.  Under carefully controlled hydrolysis conditions, either the Z or E isomer can be obtained, making this a highly attractive method for the stereoselective synthesis of substituted α,β-unsaturated aldehydes, which are difficult to access by other methods.  Furthermore, several alkynes undergo a tandem electrocyclization in-situ to provide dihydropyridine derivatives, which can be readily converted to the corresponding pyridine or piperidine compounds.