Synthesis of Fluoro‐, Monofluoromethyl‐, Difluoromethyl‐, and Trifluoromethyl‐Substituted Three‐Membered Rings

Abstract

This Minireview describes recent advances toward the synthesis of fluoro‐, monofluoromethyl‐, difluoromethyl‐, and trifluoromethyl‐substituted three‐membered rings such as cyclopropanes, aziridines, epoxides, episulfides, cyclopropenes, and 2 H‐azirines. The main synthetic methodologies since 2016 for cyclopropanes and since 2010 for the other three‐membered rings are reported.

Optimized Monofluoromethylsulfonium Reagents for Fluoromethylene-Transfer Chemistry

“…Fluoromethylation has recently been investigated, offering a single attachment point for the target substrate . However, fluoromethylene group transfer − formally offers two connection points, giving access to monofluorinated 3-membered rings . Along this line, we have recently reported on fluoromethylene transfer from S -monofluoromethyl- S -phenyl-2,3,4,5-tetramethylphenylsulfonium tetrafluoroborate ( 2a ) (Figure ) via ylide intermediate as an alternative to freon (CHFX 2 ) chemistry to access monofluorinated cyclopropane , and epoxide derivatives.…”

Recent Advances in the Synthesis of CF3‐ or HCF2‐Substituted Cyclopropanes

“…The synthetic methods appearing in the previous review may be introduced as background when necessary. During the preparation of this manuscript, Charette, Jubault and co‐workers reported a review on the synthesis of fluoro‐, monofluoromethyl‐, difluoromethyl‐, and trifluoromethyl‐substituted three‐membered rings [15] …”

“…During the preparation of this manuscript, Charette, Jubault and co-workers reported a review on the synthesis of fluoro-, monofluoromethyl-, difluoromethyl-, and trifluoromethyl-substituted three-membered rings. [15] Figure 1. HCF 2 -or CF 3 -substituted-cyclopropane-containing biologically active molecules.…”

Visible-Light-Induced Organocatalyzed [2+1] Cyclization of Alkynes and (Trifluoroacetyl)silanes

“…The incorporation of a trifluoromethyl group into organic molecules can often bring beneficial changes in chemical, physical, or biological properties. [48][49][50][51][52] Therefore, it is highly desirable to develop practical methods for introducing a CF 3 group into target compounds. Recently, we reported the first visible-light-induced [2+1] cyclization reaction of alkynes with acylsilanes for the synthesis of -trifluoromethylated cyclopropenols (Figure 1c).…”