The cooperation between two orthogonal catalytic events during the formation of carbon-carbon and carbon-heteroatom bonds has emerged as an effective strategy for enantioselective chemical synthesis. In recent years, a number of pioneering investigations have described useful chemical synthesis methods whereby the reactivity or nucleophile-electrophile combinations can be fine-tuned or extended far beyond the effect and influence of a single catalyst. The recognition of this has had profound implications for the development cooperative catalysis as a field and has provided a foundation for the development of broadly useful chemical synthesis methods. This chapter focuses on the combination of tertiary amine Lewis base and transition metal catalysts, which the authors hope will simulate further developments and advances.