Chapter 18: Aluminium-based Catalysts for Nonasymmetric Transformations

This chapter deals with the role of single-site aluminium catalysts as Lewis acids and focuses on their role in nonasymmetric reactions generating monomeric products. This overview begins with “historical” reactions like the Meerwein–Pondorf–Verley reduction as well as the reverse process, the Oppenauer oxidation. The connected Tischchenko reaction and Mukaiyama aldol synthesis as well as oxidation reactions involving hydroperoxides are also discussed. The coupling of epoxides with carbon dioxide to afford dioxolanones (cyclic carbonates) will also be addressed in this chapter due to the outstanding range of aluminium catalysts reported in this area. The central role of a skilful ligand design and the increasing complexity of ligands and catalytic systems (bifunctionality and heterogenisation of the catalyst) can be perceived as a common thread throughout this chapter.