Photoredox-Catalyzed Trifluoromethylative Intramolecular Cyclization: Synthesis of CF₃-Containing Heterocyclic Compounds

Abstract

A general photoredox-catalyzed intramolecular cyclization was developed for the synthesis of trifluoromethylated heterocyclic compounds. The reaction proceeded smoothly under mild photocatalytic conditions with high functional group tolerance, allowing the preparation of oxygen-, sulfur-, or nitrogen-containing heterocycles of different sizes. The broad substrate scope demonstrated the complexity-building potential of the strategy.

The role of photocatalysts in radical chains in homolytic aromatic substitution, radical addition to olefins, and nucleophilic radical substitution mechanisms

“…Scenarios of both processes (i.e. : oxidative [7][8][9] and reductive 10,11 ) are present in the literature. Radical chains in photoinitiated reactions [12][13][14][15] are currently postulated in the literature as well as closed catalytic loops.…”

AIBN-Induced Remote Trifluoromethyl-Alkynylation of Thioalkynes

“…Because of the significant effect of trifluoromethyl (CF 3 ) motif on improvement of metabolic stability, hydrophobicity, and bioavailability in biologically molecules, the exploration of efficient and broadly applicable trifluoromethylation methods is highly desirable in organic chemistry . In this respect, the intermolecular trifluoromethylative difunctionalization of alkynes, including halo-, oxy-, amino-, carbo-, and sulfonyltrifluoromethylation, has become an ideal and divergent method for constructing various functionalized trifluoromethylated alkenes. On the other hand, alkynes exhibit versatile reactivity and are widely used in interdisciplinary areas such as organic synthesis, chemical biology, and medicinal chemistry, and the development of alkynylation technology is of great importance.…”

Sodium Sulfite-Involved Photocatalytic Radical Cascade Cyclization of 2-Isocyanoaryl Thioethers: Access to 2-CF2/CF3-Containing Benzothiazoles

“…In the same year, MacMillan’s group realized the trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis with CF 3 SO 2 Cl. Later, Akita, Zhu, Yu, and other groups developed fluoromethylation of alkenes, isocyanides, and heteroarenes to construct fluorinated polycyclic compounds.…”