The formation of all-carbon quaternary stereocentres in acyclic systems is one of the most difficult contemporary challenges in modern synthetic organic chemistry(1,2). Particularly challenging is the preparation of all-carbon quaternary stereocentres in aldol adducts(3); this difficulty is problematic because the aldol reaction represents one of the most valuable chemical transformations in organic synthesis(4). The main problem that limits the formation of these stereocentres is the absence of an efficient method of preparing stereodefined trisubstituted enolates in acyclic systems(5-8). Here we describe a different approach that involves the formation of two new stereogenic centres-including the all-carbon quaternary one-via a combined carbometalation-oxidation reaction of an organocuprate to give a stereodefined trisubstituted enolate. We use this method to generate a series of aldol and Mannich products from ynamides with excellent diastereomeric and enantiomeric ratios and moderate yields.