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 remarkable fluorine effect on "on water" reactions is reported. The CF⋅⋅⋅HO interactions between suitably fluorinated nucleophiles and the hydrogen-bond network at the phase boundary of oil droplets enable the formation of a unique microstructure to facilitate on water catalyst-free reactions, which are difficult to realize using nonfluorinated substrates. Accordingly, a highly efficient on water, catalyst-free reaction of difluoroenoxysilanes with aldehydes, activated ketones, and isatylidene malononitriles was developed, thus leading to the highly efficient synthesis of a variety of α,α-difluoro-β-hydroxy ketones and quaternary oxindoles.

Optically active α-arylation carbonyl units are widely present in a wide variety of drugs, bioactive natural products, and valuable pharmacologically active molecules. Catalytic enantioselective α-arylation of carbonyl enolates or the related precursors with various arylating agents constitutes a powerful tactic for constructing such privileged scaffolds, which is of great interest and has gained considerable progress. This review summarizes the advances based on two major strategies with diverse arylating agents, discusses in detail the reaction mechanism, limitations, and advantages of each method and their applications, and expounds the synthetic opportunities still open for further exploration.

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.

We report a highly stereoselective synthesis of all-carbon or fluorinated tetrasubstituted alkenes from diazo reagents and fluorinated enol silyl ethers, using C-F bond as a synthetic handle. Cationic Au catalysis plays a key role in this reaction. Remarkable fluorine effects on the reactivity and selectivity was also observed.