Enantioenriched fluorinated α-and βamino acids are often encountered in numerous pharmaceuticals and bioactive molecules, and also of great importance as probes in PET and NMR for studying the behavior of enzymes and for incorporation into peptides and drug candidates. Among various synthetic strategies developed, catalytic enantioselective synthesis proves to be one of the most facile and powerful protocols to construct such privileged structures. The past decade has witnessed considerable progress in the catalytic enantioselective construction of chiral fluorinated α-and β-amino acid derivatives with structural diversity. In this review, we summarize these impressive achievements according to the bond-forming way of fluorinated α-or βamino acids, respectively, and underline the remaining challenges. This information would provide important guidance and some inspiration for the researchers engaged in organic fluorine and medicinal chemistry. nated α-Amino Acids 2.1. α-Fluoro-α-Amino Acids 2.2. α-Fluoroalkyl-α-Amino Acids 3. Catalytic Enantioselective Synthesis of Fluorinated β-Amino Acids 3.1. Electrophilic Fluorination Reactions 3.2. Mannich-Type Reactions with α-Fluorinated (Thio)Esters, Amides or Nitriles 3.3. Catalytic Asymmetric Reactions with Fluorinated Alkenes or Imines 4. Conclusion and Outlook

Azacycles such as indoles and tetrahydroquinolines are privileged structures in drug development. Reported here is an unprecedented regiodivergent intramolecular nucleophilic addition reaction of imines as a flexible approach to access N‐functionalized indoles and tetrahydroquinolines, by the control of reaction at the N‐terminus and C‐terminus, respectively. Using ketimines derived from 2‐(2‐nitroethyl)anilines with isatins or α‐ketoesters, the regioselective N‐attack reaction gives N‐functionalized indoles, while the catalytic enantioselective C‐attack reaction affords chiral tetrahydroquinolines featuring an α‐tetrasubstituted stereocenter. Mechanistic studies reveal that hydrogen‐bonding interactions may greatly facilitate such unusual N‐attack reactions of imines. The utility of this protocol is highlighted by the catalytic enantioselective formal synthesis of (−)‐psychotrimine, and the construction of various fused aza‐heterocycles.

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Catalytic asymmetric isomerization of allylic or homoallylic alcohols into synthetically useful carbonyl compounds is a redox‐neutral and 100 % atom‐economic transformation, which is of great interest and has gained increasing attention from both academic and industry. This minireview summarizes the advances in catalytic enantioselective isomerization and it involved tandem reactions over the past five years, also discusses their advantages and limitations, and expounds the synthetic chances still open for further development.

A highly enantio- and regioselective Markovnikov hydromonofluoro(methyl)alkylation of 1,3-dienes was developed using redox-neutral nickel catalysis. It provided a facile strategy to construct diverse monofluoromethyl- or monofluoroalkyl-containing chiral allylic molecules. Notably,...