Chapter 21: Lewis-base Asymmetric Organocatalysis

Addition of nucleophiles to electrophilic targets, such as carbonyl compounds or their heterocarbonyl analogues, is one of the fundamental transformations in synthetic organic chemistry. The chemistry covered in this chapter is dominated by silicon, an inexpensive and environmentally friendly element. Lewis base-catalysed asymmetric carbon–carbon bond-forming reactions that employ silicon-based nucleophiles have now reached the level of a well-established synthetic methodology. The chapter surveys the progress in the development of new efficient Lewis-base catalysts for asymmetric allylation, aldol-type reactions and desymmetrisation of meso-epoxides. Special attention is given to the mechanistic understanding of the processes and novel synthetic applications.