Liang Zhao

A practical method for the synthesis of CF ₃ -containing amino acids through visible light promoted decarboxylative cross-coupling of a redox-active ester with tert -butyl 2-(trifluoromethyl)acrylate has been developed.

Secondary trifluoromethylated alkyl bromides are versatile building blocks in the synthesis of fluorine‐containing aliphatic compounds. However, current methods of preparation are limited. In this study, we have developed a general deaminative cross‐coupling of Katritzky salts with 2‐bromo‐3,3,3‐trifluoropropene (BTP) as a route to α‐trifluoromethylated alkyl bromides that is driven by an electron‐donor‐acceptor (EDA) complex. The resultant products can be readily converted to α‐trifluoromethyl borates and α‐trifluoromethyl alcohols, enriching the current toolbox for synthesizing trifluoromethylated aliphatic compounds with wide‐ranging applications.

We presented a cascade transformation of N, N‐diallylamines and fluoroalkyl iodides into various functionalized fluoroalkylated pyrrolidines through a visible light‐induced synthetic process in the solvent‐free conditions. In this reaction system, the substrate N, N‐diallylamine acted both as the base and the electron donor. We further demonstrated the practicality of this protocol by the direct modification of amino acids and pharmaceutical molecules.

3‐Alkylated coumarins have many applications in medicinal chemistry, however, methods access to such structures are still limited. Herein, we report a site‐selective photocatalytic deaminative alkylation of coumarins utilizing pyridinium‐activated aliphatic primary amines as alkylation reagents. The protocol was highlighted by its mild reaction conditions, operational simplicity, and broad functional group compatibility. Moreover, this strategy enables late‐stage modification of some pharmaceuticals and natural products, thus providing an appealing approach to valuable molecules in medicinal chemistry. magnified image

Rencently, fluoroalkylation reactions initiated via noncovalent interaction (halogen bond or EDA complexes) have become an attractive method access to fluoro-containing compounds, and most of those reactions were promoted by visible light and stoichiometric electron-donor compounds. Here, a novel atom transfer radical addition (ATRA) reaction promoted by catalytic amount of 1,4-dimethylpiperazine at heating condition is developed. This protocol enables a simple and practical alternative for the effective iododifluoroalkylation of alkenes or alkynes, which features synthetic simplicity, wide substrate scope and feasibility of product transformations. Graphical Abstract

Fluorinated aziridines are very important structural motifs, but methods access to such structures are still very rare. In this paper, we report a mild, catalyst‐free and operationally simple strategy for the direct aminofluoroalkylation of olefins driven by the noncovalent interaction between N‐allylanilines and fluoroalkyl iodides. This photochemical transformation features synthetic simplicity, mild reaction conditions, without the use of any photoredox catalyst, and high functional group tolerance. Moreover, the structures can be used as important precursors for the synthesis of β‐fluoroalkylated alkylamine derivatives, such as fluorinated amino acids and fluorinated 2‐pyrrolidinones. magnified image

α-Trifluoromethyl alkenes can be used as peptide isosteres, moreover, the pre-installed vinyl group make it possible that transformation to diverse fluorine-containing unities. However, the cross-coupling of benzyl group with α-trifluoromethyl alkenes has yet to be developed. In this report, we describe a general method for the cross-coupling of benzylzinc reagents with 2-bromo-3,3,3-trifluoropropene (BTP) to afford diverse α-trifluoromethylalkene derivatives by using Pd(TFA)₂ as catalyst. This method takes advantage of cheap industrial available fluorine building blocks and easily prepared benzylzinc reagents to generate α-trifluoromethylalkene derivatives, which features with mild reaction conditions, wide substrate scope and feasibility of product transformations.

A simple, mild and efficient approach for the fluoroalkylation of alkenes and alkynes using 2-bromophenol as a catalyst is presented.