Tatiana Besset

Rh(III)-Catalyzed Directed C−H Olefination Using an Oxidizing Directing Group: Mild, Efficient, and Versatile

An efficient Rh(III)-catalyzed oxidative olefination by directed C-H bond activation of N-methoxybenzamides is reported. In this mild, practical, selective, and high-yielding process, the N-O bond acts as an internal oxidant. In addition, simply changing the substituent of the directing/oxidizing group results in the selective formation of valuable tetrahydroisoquinolinone products.

Diverse Strategies toward Indenol and Fulvene Derivatives: Rh-Catalyzed C−H Activation of Aryl Ketones Followed by Coupling with Internal Alkynes

The synthesis of indenols and fulvenes was achieved through Rh-catalyzed C-H bond activation of simple and diverse aryl ketone derivatives and subsequent coupling with internal alkynes. The process was found to involve either an α or γ dehydration step, depending on the substrate disposition and representing diverse pathways toward functionalized fulvenes.

Recent Progress in Direct Introduction of Fluorinated Groups on Alkenes and Alkynes by means of CH Bond Functionalization

The direct introduction of fluorine and fluorinated building blocks has recently attracted a lot of attention and particularly the direct functionalization of alkenes and alkynes. This review will highlight the major progress recently made in that field, with a focus on photocatalyzed transformations, base-promoted processes, and transition metal-catalyzed functionalization of alkenes and alkynes. Special attention will be paid to explanations of the reaction mechanisms.

Recent Progress toward the Introduction of Functionalized Difluoromethylated Building Blocks onto C(sp2) and C(sp) Centers

Fluorine chemistry is a field undergoing tremendous expansion. Although much attention has been paid to the introduction of the fluorine atom and the CF3 group, less interest has been devoted to the introduction of functionalized fluorinated building blocks, in sharp contrast with the high versatility of the fluorinated products. In this Minireview, the most relevant methods for the introduction of difluoromethylated building blocks are summarized. Access to difluoromethylated arenes, alkenes, and alkynes is highlighted and special attention is paid to explanation of the reaction mechanism.

Palladium(II)-Catalyzed Directed Trifluoromethylthiolation of Unactivated C(sp3)–H Bonds

The synthesis of trifluoromethylthiolated aliphatic acid derivatives by Pd-catalyzed C(sp(3))-H bond functionalization was developed. Using a bidentate directing group, the direct and selective introduction of a SCF3 moiety was possible on a range of amides with remarkable selectivity for C(sp(3))-centers with an electrophilic SCF3 source and pivalic acid as an additive. This work constitutes an example of the unactivated C(sp(3))-SCF3 bond formation by C-H activation offering a new access to relevant molecules.

Recent Progress in Asymmetric Fluorination and Trifluoromethylation Reactions

All domains of society are impacted by fluorine chemistry. In particular, fluorine plays a key role in medicinal, pharmaceutical and agrochemical sciences in which the synthesis and evaluation of molecules featuring one or more fluorine atoms is nowadays routine in every new discovery and development program. Since the beginning of this century, enantiopure fluorinated molecules are at the forefront of innovation of the tremendous achievements in fluorine chemistry. This review introduces the reader to the recent progress in asymmetric installation of one fluorine and a trifluoromethyl group via nucleophilic, electrophilic and radical diastereo- and enantioselective reactions.

Regio- and diastereoselective Cu-mediated trifluoromethylation of functionalized alkenes.

α- and β-substituted N,N-diethylacrylamides undergo copper-mediated direct β-trifluoromethylation. The amide moiety acts as a directing group for the regio- and the stereo-controlled introduction of the trifluoromethyl group. The reaction is carried out under acidic conditions in the presence of Umemotos reagent. This method does not require prefunctionalized substrates and delivers excellent stereoselectivity.

New entries toward the synthesis of OCF3-containing molecules

The OCF3 group is of high interest in the quest for new drugs and agrochemicals, thanks to its atypical features. This Highlight article depicts the recent and impressive advances toward the synthesis of OCF3-containing molecules.

Copper‐Mediated Formation of Aryl, Heteroaryl, Vinyl and Alkynyl Difluoromethylphosphonates: A General Approach to Fluorinated Phosphate Mimics

A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2PO(OEt)2, iodonium salts and a copper salt provided a straightforward manifold to reach these highly relevant products. The reaction proved to be highly functional group tolerant and proceeded under mild conditions, giving the corresponding products in good to excellent yields. This method represents the first general synthetic route to this important class of fluorinated scaffolds, which are well-recognized as in vivo stable phosphate surrogates.

A Straightforward and Highly Diastereoselective Access to Functionalized Monofluorinated Cyclopropanes via a Michael Initiated Ring Closure Reaction

The synthesis of highly functionalized monofluorinated cyclopropanes based on a Michael Initiated Ring Closure (MIRC) reaction has been developed. The addition of quaternary ammonium salts derived from ethyl bromofluoroacetate on a panel of electron deficient alkenes followed by cyclization gave rise to an efficient access to monofluorinated cyclopropanes with good yields and remarkable diastereoselectivity.