Enantioselective catalytic formation of tertiary stereogenic centers has nowadays reached an impressive level of maturity, as is reflected in the large variety of available methods that afford high yields and high stereoselectivities. However, the development of stereoselective approaches for the formation of quaternary stereogenic centers still represents an enormous challenge for synthetic chemists. On the other hand, biologically active molecules containing quaternary stereogenic centers provide an incentive for the development of new, selective, and useful processes. Over the last few years, breakthrough work relating to the formation of fully substituted carbon centers has appeared in the literature. In this review we discuss recent highlights of this new direction in catalysis research: the formation of quaternary stereogenic centers by enantioselective catalytic methodologies.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)