Anis Tlili

Formation of CSCF3 Bonds through Direct Trifluoromethylthiolation

For a long time, the SCF3 moiety has attracted the interest of chemists because of its intrinsic properties, including its high lipophilicity. However, until recently, the direct introduction of the SCF3 group into organic molecules has been poorly investigated, favoring indirect strategies, including the trifluoromethylation of sulfur compounds or the formation of a CF3 moiety from a precursor group that was already present in the molecule by halogen–fluorine exchange reactions. The development of new methods for the formation of C SCF3 bonds has very recently attracted the interest of several research groups. The most general and efficient methods for the attachment of SCF3 groups to carbon centers are highlighted herein. A transition-metal-free oxidative trifluoromethylthiolation of alkynes was presented by Qing and co-workers (Scheme 1). The reaction of elemental sulfur with the Ruppert–Prakash reagent (CF3SiMe3) generated the “CF3S ” species in situ, and allowed the formation of the C SCF3 bond at room temperature under air. This system supplies the products with good to excellent yields and exhibits a broad tolerance toward electron-rich and electron-poor aryl acetylene derivatives. Recently, reagent R1, which is an airand moisture-stable reagent, was successfully synthesized and used for the trifluoromethylthiolation of Grignard or Lithium reagents with good to excellent yields (Scheme 2).

Functionalization of Remote CH Bonds: Expanding the Frontier†

Novel tool set: New methodologies for the functionalization of remote CH bonds have been developed recently. In diverse approaches high selectivities are achieved for the functionalization of less reactive C(sp(2) )H as well as C(sp(3) )H bonds distal to any substituents.

Synthetic Approaches to Trifluoromethoxy-Substituted Compounds.

Because of the unique properties of the trifluoromethoxy group, molecules bearing this moiety will find applications in various fields, particularly in the life sciences. However, despite the great interest in this functional group, only a small number of trifluoromethoxylated molecules are currently synthetically accessible. Over the last few years, several innovative and promising strategies for the synthesis of trifluoromethoxylated compounds have been described. This Minireview discusses these existing methods with a particular focus on more recent advances.

More Sustainable Formation of CN and CC Bonds for the Synthesis of N-Heterocycles†

Heterocycles made green: New methodologies for the synthesis of pyrroles were recently developed based on domino Ir- and Ru-catalyzed amination and alkylations of alcohols. The concept provides a greener approach to interesting N-heterocyclic compounds.

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.

A Selective Palladium‐Catalyzed Carbonylative Arylation of Aryl Ketones to Give Vinylbenzoate Compounds

Preparation of enols: when treated with [{Pd(cinnamyl)Cl}(2)]/cataCXium A (nBuPAd(2), Ad=adamantyl) under an atmosphere of CO, aryl ketones react with aryl halides in a carbonylative C-O coupling reaction to form (Z)-vinyl benzoates.

Regioselective Ruthenium‐Catalyzed Carbonylative Direct Arylation of Five‐Membered and Condensed Heterocycles

A ruthenium-catalyzed carbonylative CH bond arylation process for the three-component synthesis of complex aryl-(hetero)aryl ketones in an aqueous solution has been developed. By exploiting the ortho-activating effect of nitrogen-containing directing groups, a regioselective, successive twofold C(sp(2))-C(sp(2)) bond formation has been achieved. This straightforward catalytic process provides access to versatile products prevalent in multiple bioactive compounds and supplies a valuable functional group for subsequent transformations.

Palladium-catalysed carbonylative α-arylation of acetone and acetophenones to 1,3-diketones.

Three COmponent -arylation: A carbonylative ketone -arylation process employing acetone for the first time, as well as acetophenones, is described (see scheme). The reaction tolerates a range of (hetero)aryl iodides and several functionalised aryl ketone coupling partners. Only low pressures of molecular CO are applied and no additional solvent is necessary.

Selective one-pot synthesis of symmetrical and unsymmetrical di- and triarylamines with a ligandless copper catalytic system

The one-pot synthesis of symmetrical or unsymmetrical di- or triarylamines using aryl iodides or bromides and LiNH(2) as ammonia source is reported. This highly selective method is based, for the first time, on a copper-catalyzed system, which does not require the presence of any additional ligand.

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.