Quentin Glenadel

Rhodium(I)-catalyzed addition of arylboronic acids to (benzyl-/arylsulfonyl)acetonitriles: efficient synthesis of (Z)-β-sulfonylvinylamines and β-keto sulfones.

An efficient rhodium(I)-catalyzed addition of arylboronic acids to (benzyl-/arylsulfonyl)acetonitrile is described. Novel β-sulfonylvinylamine products are formed in a stereoselective fashion (Z-alkene). Upon hydrolysis, useful β-keto sulfones are obtained with a broad scope of aryl and sulfonyl substituents.

Mild and Soft Catalyzed Trifluoromethylthiolation of Boronic Acids: The Crucial Role of Water

The most reactive 2nd generation of trifluoromethanesulfenamides undergoes a copper-catalyzed cross-coupling reaction with boronic acids to afford CF3 S-molecules. Contrary to the previous methods in the literature, no base addition, no heating, and no large excess of reagents are required to obtain good results. Furthermore, a crucial role of a small amount of water to favor this reaction has been demonstrated. This constitutes the mildest described conditions for such a reaction.

Benzyltrifluoromethyl (or Fluoroalkyl) Selenide: Reagent for Electrophilic Trifluoromethyl (or Fluoroalkyl) Selenolation.

Trifluoromethylseleno substituent (CF3Se) is an emerging group, but its direct introduction onto organic molecules is still quite limited and mainly restricted to nucleophilic methods. Herein, we describe a new approach to easily and safely perform electrophilic trifluoromethylselenolation starting from a simple and easily accessible reagent, namely, benzyltrifluoromethyl selenide. This strategy can be generalized to various fluoroalkylselanyl groups, even functionalized ones.

Copper-Catalyzed Perfluoroalkylthiolation of Alkynes with Perfluoroalkanesulfenamides.

Copper-catalyzed direct perfluoroalkylthiolation of alkynes by using the corresponding perfluoroalkanesulfenamide reagent is reported. The selective mono- and bis-perfluoroalkylthiolation of alkynes can be conducted under very mild conditions (no base, room temperature) in very good to excellent yields. This approach, which uses a low toxicity, inexpensive copper catalyst that incorporates a commercially available ligand, is applied in the absence of any additional base. Preliminary mechanistic investigations shed some light on the nature of the unprecedented reactivity observed.

Synthetic Approaches to Trifluoromethylselenolated Compounds

The association of trifluoromethyl group to chalcogens gives new fluorinated substituents with specific properties, mainly in term of lipophilicity. The trifluoromethylselenyl group is the last of the series that has been studied and despite pioneering approaches in the late 1960s, CF3 Se chemistry has been scarcely developed over the last decades. Some modern and efficient methods to obtain trifluoromethylselenolated molecules have recently emerged. This Review describes the advancements that have been reported.

A Metal-Free Route to Heterocyclic Trifluoromethyl- and Fluoroalkylselenolated Molecules

A metal-free methodology to easily synthesize various CF3Se-containing heterocyclic compounds has been developed through intramolecular ring closures of alkynes promoted with CF3SeCl. Moreover, this strategy has also been extended to other fluoroalkylselenyl groups.

Frontispiece: Mild and Soft Catalyzed Trifluoromethylthiolation of Boronic Acids: The Crucial Role of Water

Wet Boronic Trifluoromethylthiolation Due to their high lipophilicity, trifluoromethylthiolated molecules play an important role in various fields, in particular in life sciences. Trifluoromethylthiolation of boronic acids with a highly efficient reagent is described to obtain aromatic and vinylic trifluoromethylthiolated compounds very easily and without any specific practical skills. The crucial role of a small amount of water has been demonstrated to obtain good results. For more details see the Communication by T. Billard et al. on page 14694 ff.