This chapter chronicles the evolution of a paradigm shift in the conceptualization and development of chiral Lewis base catalysis of carbonyl addition reactions with organosilicon nucleophiles. Prior to 2000, these reactions were exclusively practiced through the agency of highly electrophilic silicon species such as allyltrichlorosilanes and enoxytrichlorosilanes derived from aldehydes, ketones, and esters. However, a serendipitous discovery made during the development of these processes led to a fundamentally new insight, namely, that silicon tetrachloride could be activated by chiral Lewis bases (primarily phosphoramides) and the resulting chiral silicenium ion could serve as a general and effective catalyst for the addition of many different enoxysilane nucleophiles derived from aldehydes, ketones, esters, nitriles, protected cyanohydrins, conjugated esters and amides, and isocyanides. In addition to providing high generality, high yield, and high stereoselectivity, the new family of Lewis base-catalyzed reactions could be investigated mechanistically, and the foundations of reactivity and selectivity could be revealed. An analysis of how this paradigm shift occurred and the circumstances that led to discovery are described.