Catalytic enantioselective electrochemical synthesis has emerged in recent years as an efficient, clean, sustainable way to obtain chiral, non-racemic molecules. The difficulties in finding reaction conditions that are compatible with the delicate functional groups of many chiral ligands and organocatalysts has hampered the developments in this field. However, the fact that very minute differences in potential can be selected, allows for fine-tuning, so that very high chemoselectivities can be achieved, which is attracting much attention. Although still few in number compared to other areas of knowledge, the existing methods allow a variety of bond-forming reactions to be performed, and very high yields and ees can be achieved. The present review surveys the literature published in the last four years.

1 Introduction

2 Transition-Metal-Catalyzed Reactions

2.1 Alkylation by C–H Bond Functionalization: C(sp³)–C(sp³) Bond Formation

2.2 C(sp³)–C(sp²) Bond Formation

2.2.1 Alkene Functionalization by Cross-Coupling Reactions

2.2.2 Arylation by Cross-Coupling Reactions

2.3 Alkynylation: C(sp³)–C(sp) Bond Formation

2.4 Cross-Coupling Reactions for the Synthesis of Axially Chiral Biaryls

2.5 Cyanofunctionalization

2.6 Miscellaneous

3 Organocatalysis

4 Conclusions