The sixth chapter of the book includes the advances achieved since 2004 in enantioselective nickel-catalysed α-halogenations, α-aminations, α-hydroxylations, α-arylations, and α-alkylations of carbonyl compounds. The last decade has seen a number of highly enantioselective nickel-catalysed electrophilic halogenation reactions to be achieved. Most of them are fluorination reactions, involving several types of carbonyl substrates. All these reactions provided near-perfect enantioselectivities by using various ligands, mostly generating quaternary stereogenic centres. On the other hand, remarkable enantioselective nickel-catalysed α-aminations of N-Boc-oxindoles with azodicarboxylates have been achieved. In the context of asymmetric α-hydroxylation reactions, while early developments required multistep procedures where the substrates were activated via enol or enolate intermediates, it has been recently demonstrated that the hydroxylation of β-keto esters could be achieved directly by using oxaziridines and chiral nickel catalysts. In the areas of α-arylations and α-alkylations, many excellent results have also been achieved. It is important to note that many of these novel reactions (halogenations, aminations, hydroxylations, as well as arylations) generated challenging quaternary carbon stereogenic centres.