Synthesis of Alpha‐trifluoromethylthio Carbonyl Compounds: A Survey of the Methods for the Direct Introduction of the SCF₃ Group on to Organic Molecules

Abstract

Scheme7.Synthesis of a-trifluoromethylthiolated spiro[4,5]trienones starting from alkynes.Scheme8.Synthesis of 2-(trifluoromethylthio)-indenones by cascade trifluoromethylthiolation/cyclization process.Scheme9.Cu II -Mediated decarboxylative trifluoromethylthiolation of a,b-unsaturated carboxylic acids.Scheme10. O-octadecyl-S-trifluoromethylthiocarbonate as SCF 3 source in the synthesis of trifluoromethylthiolated carbonyl compounds.

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

“…Depending on the type of the trifluoromethylthiolating reagent used in the chemical conversion, the methods can also be classified into three classes: radical, nucleophilic and electrophilic trifluoromethylthiolation. Some reviews in this area focused on several aspects such as the syntheses of aromatic and heterocyclic perfluoroalkyl sulfides [190], direct trifluoromethylthiolation reactions [191–194], sulfur-based fluorination and fluoroalkylation reagents [195], trifluoromethylthio cation-donating ability (Tt + DA) [196], or synthetic methods leading to compounds containing CF 3 –S units [197]. Herein, based on the transition-metal catalysis, recent research advances in these types of synthetic methods are described in this section of this review.…”

Stereoselective Synthesis of Chiral α-SCF3-β-Ketoesters Featuring a Quaternary Stereocenter

“…Trifluoromethylthiolated carbonyl derivatives are particularly attractive for their application in medicinal chemistry and as starting building block for the synthesis of functionalized molecules. However, stereoselective strategies to synthetize enantioenriched α-SCF 3 -substituted carbonyl compounds are still very rare [16].…”

“…Following our interest in the development of novel synthetic strategies for the preparation of fluorinated carbonyl derivatives [16,23], we wish to present our studies aimed to the stereoselective synthesis of α-SCF 3 -β-ketoesters featuring a quaternary stereocenter.…”

Metal-Free Alpha Trifluoromethylselenolation of Carbonyl Derivatives under Batch and Flow Conditions

“…Moreover, the high lipophilicity and high electron-withdrawing character of SeCF 3 group (Hansch lipophilicity parameter σ R = 1.29 compared to π R = 0.88 for CF 3 group) [ 16 ], make it a potential candidate for pharmaceutical and agrochemical applications. As part of our continuing interest in the development of α-chalcogen functionalization of carbonyl compounds [ 17 , 18 , 19 ] we report herein our study on the introduction of the SeCF 3 group on enols of various natures, using ClSeCF 3 as the trifluoromethylselenolating agent. In our approach, we decided to take advantage of the straightforward strategy developed by the Billard’s group for the in preparation of the highly reactive ClSeCF 3 reagent [ 20 ] and studied both the in-batch and the unprecedented in-flow transformation.…”