This Review summarizes the advances in the construction of all-carbon quaternary stereocenters via catalytic enantioselective desymmetrization of prochiral and meso-compounds, highlights the power and potential of this strategy in the total synthesis of natural products and biologically active compounds, and outlines the synthetic opportunities still available.

The catalytic enantioselective assembly of spirocyclic molecules featuring a spiro quaternary carbon stereocenter is currently of great interest because such privileged 3D structures are widely present in natural products that exhibit a broad spectrum of biological and pharmacological activities. This review summarizes the advances based on six major synthetic strategies and showcases the reaction mechanisms in detail. The advantages and limitations of each synthetic strategy are presented, and the remaining synthetic opportunities are outlined.

A highly enantioselective Strecker reaction of difluoromethyl and trifluoromethyl ketoimines was developed. Remarkable fluorine effect on the reactivity and selectivity is observed and discussed.

Sulfur-containing tetrasubstituted carbon stereocenters are widely present in natural products, drugs, and biologically active compounds. Catalytic enantioselective construction of such fully substituted carbon stereocenters is a current research interest, with four major synthetic strategies being developed. This review summarizes the advances in this field, discusses in detail the advantages and limitation of each synthetic strategy, and outlines the synthetic opportunities still open for development.