Tatiana Besset

Tatiana Besset
Université de Rouen | UR · Organic Chemistry research Institute

Catalysis, Organic Chemistry, Organofluorine Chemistry, Organometallic chemistry

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98
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Introduction

Publications

Publications (98)
Article
The unprecedented Pd‐catalyzed (ethoxycarbonyl)difluoromethylthiolation reaction of various unsaturated derivatives was studied. In the presence of the (ethoxycarbonyl)difluoromethylsulfenamide reagent I and under mild reaction conditions (60 °C), both 2‐(hetero)aryl and 2‐(a‐aryl‐vinyl)pyridine derivatives were smoothly functionalized with this me...
Article
α-Fluorinated acrylates could act as Michael acceptors and become a platform toward the synthesis of relevant complex molecules. Very few conjugate additions have been developed in the literature with these specific substrates, and herein, we reported the first phospha-Michael addition (PMA) on α-trifluoromethylacrylates and α-fluoromethylacrylates...
Article
In this study, a practical and straightforward synthesis of β‐( E )‐trifluoromethylstyrenes by ruthenium‐catalyzed C‐H bond activation was developed. The readily available and inexpensive 2‐bromo‐3,3,3‐trifluoropropene (BTP), a non‐ozone depleting reagent, was used as a reservoir of 3,3,3‐trifluoropropyne. With this approach, the monofunctionalizat...
Article
In the field of organofluorine chemistry, the quest for emergent fluorinated groups is in high demand. In particular, the scientific community has shown special interest in the SCF3 residue thanks to its unique properties. Indeed, over the last decade, the SCF3 group has become a pivotal fluorinated moiety, as demonstrated by several SCF3-containin...
Article
An approach for the distal construction of a C(sp3)‐SCF2R bond on aliphatic alcohols enabled by 1,5‐hydrogen‐atom transfer (HAT) was developed. In the presence of a hypervalent iodine (PIDA) and readily available ArSO2SCF2R reagents, this transition metal‐free approach allowed the remote functionalization of a broad variety of alcohols with emergen...
Article
The synthesis of an original electrophilic difluoromethylating reagent was successfully achieved upon a straightforward protocol (3 steps). Like a Swiss army knife, this bench-stable reagent allowed the functionalization of various classes of compounds under mild and transition metal-free conditions. Hence, an efficient and operationally simple too...
Article
The synthesis of bench‐stable electrophilic thiocyanating reagents was depicted in two steps from readily available starting materials in good yields. These newly‐designed electrophilic reagents were successfully applied for the thiocyanation of different nucleophiles under mild and transition metal‐free conditions. Preliminary experiments for the...
Article
A library of original and shelf-stable reagents, source of the (ethoxycarbonyl)difluoromethylthio group, is reported. These reagents are applied to the functionalization of a large panel of aldehydes via a transition metal-free protocol under mild reaction conditions. This approach offers an efficient access to valuable difluoromethylthioester deri...
Article
A straightforward 2,2,2-trifluoroethylation of acrylamides by Pd-catalyzed C-H bond activation was reported by using a fluorinated hypervalent iodine reagent as a coupling partner. At room temperature, this additive-free approach allowed the synthesis of Z-2,2,2-trifluoroethylated acrylamides (19 examples, up to 73% yield) in a stereoselective mann...
Article
The review aims at providing an overview on the developments made in hydrogenation reactions of molecules having various fluorinated groups (F, CF3, CF2H, CF2Rf). Indeed, the hydrogenation of fluorine-containing molecules is a straightforward and atom-economical way to access challenging (chiral) fluorinated scaffolds. This promising field is still...
Article
The regioselective 2,2,2‐trifluoroethoxylation at the C5 position of amides derived from the 8‐aminoquinoline has been developed. In the presence of PIDA, an unprecedented and undirected transition metal‐free transformation was achieved using the readily available and appealing 2,2,2‐trifluoroethanol as the fluorinated source. The selective distal...
Article
Sulfur‐ and selenium‐containing compounds can be accessed by using electrophilic reagents. Read more about recent advances of synthetic pathways to get SCN‐ and SeCN‐containing molecules in the Minireview by T. Besset et al. on page 6145.
Article
Organothiocyanate and organoselenocyanate compounds are of paramount importance in organic chemistry as they are key intermediates to access sulfur‐ and selenium‐containing compounds. Therefore, among the different synthetic pathways to get SCN‐ and SeCN‐containing molecules, original methodologies using electrophilic reagents has recently been exp...
Article
In this manuscript, a simple and efficient sulfa-Michael addition reaction of aryl thiols to trisubstituted α-fluoro-α,β-unsaturated esters both in racemic and, for the first time, in enantioselective version is reported. The commercially available dimer of cinchona derivatives (DHQ)2PYR was used as a catalyst. This strategy showed a great toleranc...
Article
In this Letter, the transition-metal-catalyzed chlorination of alkenes is reported. In the presence of the commercially available and inexpensive N-chlorosuccinimide and without additive, the Pd-catalyzed chlorination of acrylamides by C-H bond activation was developed at room temperature under air. Under these mild reaction conditions, the versati...
Article
Organofluorine chemistry in the focus: Novel transformations based on a radical process were designed recently, offering new synthetic tools for the selective functionalization of unactivated C(sp³)−H bonds with a fluorinated group at a remote position to a functional group. This Minireview highlights these recent advances based on a 1,5‐hydrogen a...
Article
Full-text available
The Pd‐catalyzed directed thiocyanation reaction of arenes and heteroarenes by C−H bond activation was achieved. In the presence of an electrophilic SCN source, this original methodology offered an efficient tool to access a panel of functionalized thiocyanated compounds (21 examples, up to 78 % yield). Post‐functionalization reactions further demo...
Article
Full-text available
Over the years, the development of new methodologies for the introduction of various fluorinated motifs has gained a significant interest due to the importance of fluorine-containing molecules in the pharmaceutical and agrochemical industries. In a world eager to eco-friendlier tools, the need for innovative methods has been growing. To address the...
Chapter
In the past decade, tremendous advances have been made regarding the development of new sulfur‐containing fluorinated groups. Indeed, the quest for original fluorinated residues and especially those bearing a functional group that can be either modulated or directly used in drug discovery program is appealing. Among them, a strong interest was dedi...
Article
An unprecedented remote and regioselective trifluoromethylthiolation reaction of alcohols was developed. Under mild conditions, a panel of free-alcohols was selectively functionalized with TolSO2SCF3 reagent as the SCF3 source in the presence of hypervalent iodide (PIDA) under blue light irradiation. This approach offered an operationally simple to...
Article
In this manuscript, the synthesis of an original SCF2PO(OEt)2‐containing reagent was depicted. Thanks to the unique properties of this newly‐designed source, an unprecedented transformation with aldehydes was conducted under radical conditions, offering an access to high value‐added fluoroalkylthio compounds. Preliminary mechanistic studies were co...
Article
The diverse reactivity of NHCs in organocatalysis is due to the possibility of different modes of action. Although NHC‐bound enolates and dienolates are known, the related NHC‐bound cross‐conjugated aza‐trienolates remain elusive. Herein, we demonstrate the NHC‐catalyzed formal [6+2] annulation of nitrogen‐containing heterocyclic aldehydes with tri...
Article
A new methodology was developed to access isothiazolone derivatives from simple acrylamides by transition metal catalyzed C-H bond functionalization. This Pd-catalyzed reaction using an electrophilic SCN source offered an efficient tool to access a panel of functionalized isothiazolone derivatives (21 examples, up to 71% yield).
Article
A continuous flow process for the synthesis of trifluoromethylthioethers is reported. The palladium-catalyzed C-H trifluoromethylthiolation of amides derived from the 8-aminoquinoline using N-[(trifluoromethyl)thio]phthalimide produced the desired products in moderate to good yields with a residence time of 20 min. In comparison with the batch proc...
Article
Full-text available
Fluorine-containing molecules are compounds of interest in materials as well as in pharmaceutical and agrochemical industries. Therefore, developments in that research field are tremendous and a special focus was dedicated to the design and the study of emergent fluorinated groups. In particular, the CF2Me residue is attractive as it could be used...
Article
In recent years, a renewal of interest was showed to the quest of new synthetic solutions to directly introduce emergent fluorinated groups (SRf) onto molecules. In this context, a new generation of reagents (ArSO2SRf) as efficient sources of SCF3, SCF2H and more generally SRf groups, was designed. Hence, potent solutions was developed for the synt...
Article
In this guest editorial Tatiana Besset, Gerard McGlacken, and Michael Schnürch introduce the European COST Action “C–H Activation in Organic Synthesis (CHAOS)”. In this guest editorial Tatiana Besset, Gerard McGlacken, and Michael Schnürch introduce the European COST Action “C–H Activation in Organic Synthesis (CHAOS)”.
Article
Functionalization of the indole N-H bond for enantioselective synthesis of biologically important pyrroloquinoline derivatives has been reported under oxidative N-heterocyclic carbene catalysis conditions. The interception of catalytically generated chiral α,β-unsaturated acylazoliums with the indole derivatives proceeds in an aza-Michael/Michael/l...
Article
In this study, a general approach towards the synthesis of trifluoromethylthiolated olefinic and aromatic compounds was developed. Under Pd‐catalysis, the direct introduction of a SCF3 group was realized in the presence of the Munavalli reagent as the electrophilic SCF3 source and in the absence of additives. A large number of acrylamides and aroma...
Article
Here we reported a Pd-catalyzed coupling reaction between acrylate derivatives and BTP (2-bromo-3,3,3-trifluoropropene) to access 3-trifluoromethylated 1,3-dienes. The reaction allows the formation of the corresponding products in good to excellent yields and moderate Z/E diastereoisomeric ratios. This method broadens the current toolbox to access...
Article
Full-text available
The present review is devoted to summarizing the recent advances (2015–2017) in the field of metal-catalysed group-directed C–H functionalisation. In order to clearly showcase the molecular diversity that can now be accessed by means of directed C–H functionalisation, the whole is organized following the directing groups installed on a substrate. I...
Article
In this study, a straightforward methodology was developed to access quaternary α‐trifluoromethylthiolated chloroaldehydes. Using the Munavalli reagent as the electrophilic SCF3 source, a base‐catalyzed trifluoromethylthiolation reaction with a panel of α‐chloroaldehydes was successfully achieved under mild reaction conditions. The α‐trifluoromethy...
Article
Herein the synthesis of a novel bench stable electrophilic reagent to construct the OCFHMe motif from O-nucleophiles was described. This sulfonium salt, readily obtained in 5 steps, reacted with various...
Article
We report the palladium-catalyzed introduction of the di­fluoromethylposphonate unit onto aryl and heteroaryl iodides under mild conditions. Using the CuCF 2 PO(OEt) 2 species generated in situ, the method allows the functionalization of various otherwise reluctant substrates. In addition, this reaction permits the formation of CF 2 PO(OEt) 2 -cont...
Article
The Pd-catalyzed diastereoselective trifluoromethylthiolation of acrylamides was developed to allow the formation of the Z-isomer as a single product. Using a C–H bond functionalization strategy, the method was applied to a broad range of α-aryl, α-alkyl, and α,β-disubstituted acrylamides bearing the amide derived from the 8-aminoquinoline as a dir...
Article
Herein, we reported a general procedure to access CF2PO(OEt)2-containing molecules. Thanks to a simple protocol to prepare the CuCF2PO(OEt)2 reagent, a broad range of substrates was functionalized. The procedure allowed to convert aryl diazonium salts as well as aryl, heteroaryl, vinyl and alkynyl iodonium salts into the corresponding fluorinated m...
Article
In recent years, the C–H bond activation field has known very fast expansion offering valuable synthetic tools. Consequently, the quest for new approaches to afford atom- and step-economical processes has driven the scientific community to imagine original strategies. In this context, the direct functionalization of substrates by a transition-metal...
Article
Herein the synthesis of various SCF218F-containing derivatives is reported by a transition metal-free process. By using HCF218F, readily generated from a bench-stable difluoromethyl sulfonium salt, various aromatic disulfides were easily converted into the desired radiolabelled trifluoromethylthiolated compounds in the presence of a base. This prot...
Article
A palladium-catalyzed C-H bond functionalization of acrylamides was developed to build up stereoselectively trifluoromethylated 1,3-butadienes. Using a tertiary amide as a directing group, olefins were selectively functionalized with 2-bromo-3,3,3-trifluoropropene to access these important fluorinated compounds. The methodology was extended to the...
Article
We report herein a straightforward access to α-(diethyl phosphono)difluoromethylthiolated ketones. The methodology involving the nucleophilic [Cu]CF2PO(OEt)2 species allowed the formation of the targeted compounds in moderate to high yields using a simple procedure. This method represents a convenient alternative to the known approaches to introduc...
Article
Herein, we report a copper salt-controlled divergent reactivity toward α-diazocarbonyl compounds. By a simple change of the copper counteranion under identical reaction conditions, the reported method allowed an easy access to either (Z)-α-fluorovinylphosphonate or alkyl-SCF2 PO(OEt)2 derivatives in good yields. Mechanistic studies were performed a...
Article
Herein, we report a copper salt-controlled divergent reactivity toward α-diazocarbonyl compounds. By a simple change of the copper counteranion under identical reaction conditions, the reported method allowed an easy access to either (Z)-α-fluorovinylphosphonate or alkyl-SCF2PO(OEt)2 derivatives in good yields. Mechanistic studies were performed an...
Article
In recent years, much interest has been paid to difluoromethylthiolated molecules as the "SCF2 " moiety is a key motif in drug and agrochemical research. Consequently, the development of versatile strategies for the selective synthesis of SCF2 H- and SCF2 FG-containing molecules (FG=functional group) has attracted a lot of attention and inspired th...
Article
An unprecedented electrophilic difluoromethylthiolating reagent (MesNHSCF2PO(OEt)2) was designed. Under mild and metal-free conditions, this new reagent reacted with various nucleophiles, thus offering an efficient and operationally simple tool for the construction of C?SCF2PO(OR)2, N?SCF2PO(OR)2, and S?SCF2PO(OR)2 bonds. Finally, thanks to this ne...
Article
An unprecedented electrophilic difluoromethylthiolating reagent (MesNHSCF2PO(OEt)2) was designed. Under mild and metal-free conditions, this new reagent reacted with various nucleophiles, thus offering an efficient and operationally simple tool for the construction of C?SCF2PO(OR)2, N?SCF2PO(OR)2, and S?SCF2PO(OR)2 bonds. Finally, thanks to this ne...
Article
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.
Article
A practical and efficient one-pot oxidative trifluoromethylthiolation of primary and secondary amines under mild conditions is presented.
Article
The difluoromethyl phosphonate motif plays a crucial role in the development of bioactive molecules as it is considered as a phosphate bioisoster. Since 2010, a renewal of interest to enlarge the panel of reactions to access these difluoromethylated phosphonate-containing molecules has been witnessed. This Concept article charts the recent progress...
Article
A Pd-catalyzed directed chlorination of unactivated C(sp3)-H bonds has been developed. By using the bidentate 8-aminoquinolinyl directing group, selective chlorination of aliphatic amides has been achieved in moderate to good yields at room temperature in the presence of N-chlorosuccinimide (NCS). This approach offers access to valuable chlorinated...
Article
The first successful introduction of an α-trifluoromethylvinyl group via directed C—H bond functionalization is described.
Article
Herein, we described a practical and efficient one-pot oxidative trifluoromethylthiolation of amines. A panel of primary and secondary amines was functionalized in good yields at room temperature. This general approach was further applied to the thiocyanation of anilines and the corresponding products can be readily used as SCN electrophilic source...
Article
We report the first introduction of 2-bromo-3,3,3-trifluoropropene (BTP) by directed C-H bond functionalization. The developed method gives straightforward access to α-(trifluoromethyl)styrene derivatives without prior prefunctionalization of the substrates. This palladium-catalysed transformation was applied to a broad range of substrates, and the...
Article
A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2 PO(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...
Article
Over the last years, the organofluorine chemistry field has known a very fast expansion offering to the scientific community a panel of efficient tools for the synthesis of fluorinated molecules. Despite these recent advances, the 1,4-addition of nucleophilic fluorinated groups onto Michael-type acceptors to construct Rf-containing C(sp3) center is...
Article
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...
Article
The alkynylcopper substrates are prepared as yellow solids and directly used in the reaction with the inexpensive ester (II) under mild conditions.
Article
The synthesis of trifluoromethylthiolated aliphatic acid derivatives by Pd-catalyzed C(sp3)-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(sp3)-centers with an electrophilic SCF3 source and pivalic a...
Article
The direct vicinal difunctionalization of versatile alkynes is an area of considerable interest. In particular, the concomitant introduction of a functional group and a fluorinated moiety offers new efficient synthetic routes to the construction of highly functionalized olefins, key building blocks in the synthesis of several complex and relevant m...
Article
A copper-mediated fluorofunctionalization of alkenes and alkynes has been developed. This method provides ready access to trisubstituted difluoromethylated olefins (from dihydropyrans, glycal derivatives, or terminal alkynes) or to tetrasubstituted olefins (from disubstituted alkynes). The products were obtained in good to high yields with acceptab...
Article
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...
Article
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-c...
Article
An efficient synthesis of difluoromethylated alkynes is described. A panel of readily available CuI acetylides undergo direct difluoromethylation by using BrCF2CO2Et, which is an inexpensive, easy to handle, commercially available fluorinated reagent. The reaction, which is based on a Castro–Stephens transformation, proceeds smoothly under mild con...
Article
The amination of racemic α-chiral aldehydes, 2-phenylpropanal derivatives, was investigated employing ω-transaminases. By medium and substrate engineering the optical purity of the resulting β-chiral chiral amine could be enhanced to reach optical purities up to 99% ee. Using enantiocomplementary ω-transaminases allowed us to access the (R)- as wel...
Patent
Full-text available
Modification of a unique supramolecular assembly of a pyridylphosphine ligand and a metal centered porphyrin complex is shown to give unprecedented selectivities to branched aldehydes via rhodium catalyzed hydroformylation of propylene and 1-octene. Use of magnesium in the porphyrin center provides the highest reported concentrations of iso-butyral...
Patent
Full-text available
Use of a unique supramolecular assembly of a pyridylphosphine ligand and a metal centered porphyrin complex is shown to give unprecedented selectivities to branched aldehydes via rhodium catalyzed hydroformylation of unsubstituted linear alpha-olefins such as propylene and 1-octene. Increasing the syngas pressure is shown to have a beneficial effec...
Article
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, en...
Article
This review provides a detailed overview on the research carried out in self-assembled supramolecular capsules enabling encapsulation of transition metals within their inner space. The supramolecular assemblies discussed are based on cationic/anionic interactions between cone-shaped building blocks, derived from quaternary ammonium and sulfonated s...
Article
Alpha- and beta-substituted N,N-diethylacrylamides undergo copper-mediated direct beta-trifluoromethylation. The amide moiety acts as a directing group for the regio- and the stereocontrolled introduction of the trifluoromethyl group. The reaction is carried out under acidic conditions in the presence of Umemoto's reagent. This method does not requ...
Article
Working together: The presence of a remote directing group on terminal 1,1-diaryl and 1,1-dialkyl alkenes led to high and unprecedented enantioselectivity in iridium-catalyzed asymmetric hydrogenation. This strategy offers efficient synthetic pathways towards valuable enantiomerically enriched 1,1-diaryl and 1,1-dialkyl alkanes. Moreover, the direc...
Article
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 cyclop...
Article
Zusammenwirken: Das Vorhandensein einer dirigierenden Gruppe abseits terminaler 1,1‐Diaryl‐ und 1,1‐Dialkylalkene führte bei der iridiumkatalysierten asymmetrischen Hydrierung zu einer beispiellosen Enantioselektivität (siehe Schema). Diese Verfahrensweise ermöglicht wirksame Synthesen von nützlichen enantiomerenangereicherten 1,1‐Diaryl‐ und 1,1‐D...
Article
Full-text available
The use of the commercially available, bifunctional phosphine 1,3,5-triaza-7-phosphaadamantane (abbreviated as PN3) in conjunction with a series of Zn(salphen) complexes leads to sterically encumbered phosphine ligands as a result of (reversible) coordinative Zn-N interactions. The solid state and solution phase behaviour of these supramolecular li...
Article
This study reveals that, in contrast to expectations, supramolecular encapsulated rhodium catalysts can be used at industrially relevant temperatures (75–80 °C), providing highly active catalysts. The unprecedented regioselectivity for the branched aldehydes can be retained if high carbon monoxide (CO) concentrations are used.
Article
In the last few years, Rh(III)-catalyzed CH functionalizations have made tremendous progress and, consequently, have recently received increasing attention. These CH activation reactions, generally involving a chelate assisting directing group, have been utilized to form valuable heterocycles and to run useful coupling reactions. In this paper, thr...
Article
A tri-ing transformation: The increasingly high demand for trifluoromethylated arenes and heteroarenes is a major challenge that has been addressed through the development of trifluoromethylation reactions. Several effective approaches for late-stage trifluoromethylation, as well as the use of practical and cheap trifluoromethylation reagents are h...
Article
Vielversprechendes: Der immer größer werdende Bedarf an trifluormethylierten Arenen und Heteroarenen stellt eine große Herausforderung dar, der mit der Entwicklung von Trifluormethylierungsreaktionen begegnet wurde. In diesem Highlight werden mehrere effektive Ansätze für die Trifluormethylierung im späten Reaktionsstadium und die Verwendung von ei...