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

A good EG: Ethylene glycol (EG) is a catalyst‐free medium that can promote the highly efficient Strecker reaction of α‐CF2H or α‐CF3 ketoimines and TMSCN. EG was used in several reactions, including the catalyst‐free Morita–Baylis–Hillman reaction.

Herein we report the first versatile and expeditious method for the site-selective C−H fluoromethylation of aryl iodides via Pd/norbornene cooperative catalysis, which could work as a robust toolbox for the diversity-oriented synthesis (DOS) of fluoromethylated arenes. This methodology features the use of the low-cost industrial raw material CH 2 IF as the fluoromethyl source, an excellent functional group tolerance, and a broad ipso termination scope and can be expanded to the late-stage modification of biorelevant molecules.

Although trifluoromethyl alkenes have great synthetic potential, their 1,2-difunctionalization has been a challenge. In this Letter, we disclose the first 1,2-dicarbofunctionalization of trifluoromethyl alkenes with pyridinium salts via a cascade process involving a base-promoted [3 + 2] cycloaddition followed by a visible-light-mediated Norrish-type-II fragmentation. This protocol allows for the formation of pyridines bearing a trifluoromethyl-substituted quaternary center in moderate to excellent yields under mild conditions.

Indole derivatives are important heterocycles in organic synthesis for serving as privileged building blocks for functional material and as key components in a lot of bioactive compounds. Propargylic alcohols, bearing alkynyl and hydroxyl functional groups, have emerged as promising feedstock materials for the construction of carbo-and heterocycles. Especially, in the last decade, the Lewis or Brønsted acid catalysed tandem annulations of propargylic alcohols to build structurally diverse indole derivatives have been well-investigated. In this review, we summarize two main synthetic strategies toward indole derivatives via the cascade reactions of propargylic alcohols: indole-ring formation involved tandem reactions and the direct function-alization of indole skeletons. We hope this review would help to develop new and more efficient protocols for the synthesis of indole-included N-heterocycles. Direct Functionalization of Indole Skeletons 3.1. Reactions Initiated with Prior Activation of the Alkyne Moiety 3.2. Reactions Initiated with Prior Activation of the Hydroxyl Group 4. Conclusions