Dmitry Katayev

• Doctor of Philosophy
• Professor (Assistant) at University of Bern

Herein, we present an efficient and practical method for multicomponent carbo-heterofunctionalization of alkenes via radical-polar crossover photoredox catalysis. Employing geminal bromonitroalkanes as redox-active reagents with a wide range of O-centered nucleophiles allows rapid access to various 1,3- difunctionalized nitro compounds, including β...

The evolution of catalysis and functional group transfer reagents play a significant role in the development of anti‐Markovnikov alkene hydrofunctionalization reactions, facilitating the access to value‐added molecules. We herein report the first rational design of a modular intermolecular anti‐Markovnikov hydronitration of alkenes, enabling the di...

The growing demand for chemical production continues to drive the development of sustainable and efficient methods for introducing molecular complexity. In this context, the exploration of unconventional functional group transfer reagents (FGTRs) has led to significant advancements in practical and atom-efficient synthetic protocols. Aiming to adva...

Fluorine's high electronegativity, lipophilicity, and metabolic stability make it a valuable element for drug design and development. Consequently, significant synthetic efforts have focused on introducing fluorine and fluorinated motifs into organic molecules, with the synthesis of trifluoromethyl ketones (TFMKs) recently attracting considerable a...

Nitrate esters hold pivotal roles in pharmaceuticals, energetic materials, and atmospheric processes, motivating the development of efficient synthesis routes. Here, we present a novel catalytic method for the synthesis of nitrates via the direct O‐nitration of alcohols, addressing limitations of current traditional methods. Leveraging bench‐stable...

Nitrate esters hold pivotal roles in pharmaceuticals, energetic materials, and atmospheric processes, motivating the development of efficient synthesis routes. Here, we present a novel catalytic method for the synthesis of nitrates via the direct O‐nitration of alcohols, addressing limitations of current traditional methods. Leveraging bench‐stable...

Herein we present our studies on the solvent-controlled difunctionalization of alkenes utilizing chlorodifluoroacetic acid (CDFA) and α-halo carboxylic acids for the synthesis of γ-lactones, γ-lactams and α,α-difluoroesters. Mechanistic insights revealed that photocatalytic reductive mesolytic cleavage of the C–X bond delivers elusive α-carboxyl al...

A general and modular protocol is reported for olefin difunctionalization through mechanochemistry, facilitated by cooperative radical ligand transfer (RLT) and electron catalysis. Utilizing mechanochemical force and catalytic amounts of 2,2,6,6‐tetramethylpiperidinyloxyl (TEMPO), ferric nitrate can leverage nitryl radicals, transfer nitrooxy‐funct...

Nitro compounds play a crucial role in academia and industries, serving as building blocks for the synthesis of drugs, agrochemicals, and materials. Nitration, a fundamental process in organic synthesis, has undergone significant evolution since the 19th century. While electrophilic nitration dominates historically, recent decades have seen a focus...

We highlight key contributions in the field of direct radical CAr− H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into thr...

We highlight key contributions in the field of direct radical CAr–H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into thre...

Herein, we report the rational design of a modular dual photoredox and cobalt catalysis paradigm for the difunction-alization of unsaturated hydrocarbons, unlocking the synthesis of a valuable but challenging 1,2-halonitroalkane substrate class. The protocol relies on the use of the redox-active organic nitrating reagent N-nitrosuccinimide as a sou...

Nitroaromatic compounds represent one of the essential classes of molecules that are widely used as feedstock for the synthesis of intermediates, the preparation of nitro‐derived pharmaceuticals, agrochemicals, and materials on both laboratory and industrial scales. We herein disclose the efficient, mild, and catalytic ipso‐nitration of organotrime...

Nitroaromatic compounds represent one of the essential classes of molecules that are widely used as feedstock for the synthesis of intermediates, the preparation of nitro‐derived pharmaceuticals, agrochemicals, and materials on both laboratory and industrial scales. We herein disclose the efficient, mild, and catalytic ipso‐nitration of organotrime...

Herein, we introduce an electrochemically assisted generation of nitryl radicals from ferric nitrate under mild reaction conditions using a simple setup with inexpensive graphite and stainless‐steel electrodes. The mechanism of the reaction is supported by detailed spectroscopic and experimental studies. Powered by electricity and driven by electro...

Hiermit stellen wir einen elektrochemisch unterstützten Prototypen für die Erzeugung von Nitrylradikalen aus Eisen(III)‐nitrat unter milden Reaktionsbedingungen vor, wobei eine einfache Vorrichtung mit kostengünstigen Graphit‐ und Edelstahlelektroden verwendet wurde. Die einzigartige Reaktionsweise wurde durch detaillierte spektroskopische und expe...

We report the development of a practical photocatalytic strategy to access various nitro‐containing cyclic compounds from olefins via semipinacol‐type rearrangement, cycloetherification, and lactonization reactions, employing N‐nitrosuccinimide as a bench‐stable, non‐metal‐based nitrating reagent. Mechanistic insights suggest that this light‐driven...

The incorporation of the gem‐difluoromethylene (CF2) group into organic frameworks is highly sought due to the influence of this unit on the physicochemical and pharmacological properties of molecules. Herein we report an operationally simple, mild, and switchable protocol to access various gem‐difluoro compounds that employs chlorodifloroacetic an...

The incorporation of the gem ‐difluoromethylene (CF 2 ) group into organic frameworks is highly sought due to the influence of this unit on physicochemical and pharmacological properties of molecules. Herein we report an operationally simple, mild, and switchable protocol to access various gem ‐difluoro compounds that employs chlorodifloroacetic an...

The outstanding impact of fluorine atom in drug discovery cannot be overestimated. Substantially, the incorporation of the gem-difluoro (CF2) group into organic frameworks is highly sought due to the influence of this unit on physicochemical and pharmacological properties of molecules. Yet, introduction of CF2 moiety into organic structures is a st...

The outstanding impact of fluorine atom in drug discovery cannot be overestimated. Substantially, the incorporation of the gem-difluoro (CF2) group into organic frameworks is highly sought due to the influence of this unit on physicochemical and pharmacological properties of molecules. Yet, introduction of CF2 moiety into organic structures is a st...

Nitro compounds are vital raw chemicals that are widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, and materials. Thus, nitrating reactions are of great importance for chemists and are even taught in schools as one of the fundamental transformations in organic synthesis. Since the discovery of...

Nitro compounds are vital raw chemicals that are widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, and materials. Thus, nitrating reactions are of great importance for chemists and are even taught in schools as one of the fundamental transformations in organic synthesis. Since the discovery of...

We report a mild and operationally simple trifluoroacylation strategy of olefines, that utilizes trifluoroacetic anhydride as a low‐cost and readily available reagent. This light‐mediated process is fundamentally different from conventional methodologies and occurs through a trifluoroacyl radical mechanism promoted by a photocatalyst, which trigger...

Here we report a mild and operationally simple trifluoroacylation strategy of olefines, that utilizes trifluoroacetic anhydride as a low‐cost and readily available reagent. This light‐mediated process is fundamentally different from conventional methodologies and occurs through a trifluoroacyl radical mechanism promoted by a photocatalyst, which tr...

Trifluoromethyl ketones are not only found in drug like substances, but are also considered as key synthons for the preparation of various fluorinated heterocyclic molecules. Access to such trifluoromethyl ketone derivatives typically requires the incorporation of the trifluoromethyl group, or a surrogate moiety, at the beginning of a multi-step sy...

Perfluoroalkylated α‐amino acids (PFAAs) are a unique class of compounds for biochemistry and pharmaceutical science. In this context, we report the successful intermolecular coupling of the Belokon’s chiral dehydroalanine Ni(II) complex with a variety of perfluoroalkyl iodides. A 4‐cyanopyridine/B 2 Pin 2 catalytic system generates perfluoroalkyl...

Herein, the synthesis and characterization of a hypervalent‐iodine‐based reagent that enables a direct and selective nitrooxylation of enolizable C−H bonds to access a broad array of organic nitrate esters is reported. This compound is bench stable, easy‐to‐handle, and delivers the nitrooxy (‐ONO2) group under mild reaction conditions. Activation o...

Organische Salpetersäureester wurden mit einem auf einer hypervalenten Iodverbindung basierenden Nitrooxylierungsreagenz hergestellt. Die vielfältige Reaktivität unter verschiedenen Reaktionsbedingungen wurde im Rahmen der Synthese nitrooxylierter β‐Ketoester, Malonate, 1,3‐Diketone und Oxindole unter milden Bedingungen demonstriert. Abstract Die...

Photocatalytic and metal-free protocols to access various aromatic and heteroaromatic nitro compounds through ipso-nitration of readily available boronic acid derivatives were developed using non-metal-based, bench-stable, and recyclable nitrating reagents. These methods are operationally simple, mild, regioselective, and possess excellent function...

The nitro group (NO2) is a key functional group in chemistry architecture. In the Full Paper by D. Katayev et al. on page 12929 ff., a new methodology is described for the activation of N‐nitrosuccimide for the direct synthesis of β‐nitroalkenes, β‐nitrohydrins, β‐nitroethers, isoxazolines and isoxazoles. By using of cyclic voltammetry, photophysic...

We leverage the slow liberation of nitrogen dioxide from a newly discovered, inexpensive succinimide‐derived reagent to allow for the C−H diversification of alkenes and alkynes. Beyond furnishing a library of aryl β‐nitroalkenes, this reagent provides unparalleled access to β‐nitrohydrins and β‐nitroethers. Detailed mechanistic studies strongly sug...

Nitroaromatics and nitroheteroaromatics serve as key building blocks and intermediates in synthesis, and form the core scaffold of a vast number of materials, dyes, explosives, agrochemicals and pharmaceuticals. However, their synthesis relies on harsh methodologies involving excess mineral acids, which present a number of critical drawbacks in ter...

Demonstrated herein is the construction of trifluoromethylated quaternary carbon centers by an asymmetric radical transformation. Enantioenriched trifluoromethylated oxindoles were accessed using a hypervalent iodine‐based trifluoromethyl transfer reagent in combination with a magnesium Lewis acid catalyst and PyBOX‐type ligands to achieve up to 99...

We demonstrate the construction of trifluoromethylated quaternary carbon centers via an asymmetric radical transformation. Enantioenriched trifluoromethylated oxindoles were accessed through the use of a hypervalent iodine‐based trifluoromethyl transfer reagent in combination with a magnesium Lewis acid catalyst and PyBOX‐type ligands to achieve up...

The introduction of halogenated functional groups by hypervalent iodine(III) reagents has proven to be a popular synthetic method in modern organic chemistry. Such diverse and often unique chemical behavior of iodine(III) compounds originates from their structural and bonding features. In this chapter, we aim to discuss the key structural propertie...

Phase‐transfer‐catalyzed regioselective nucleophilic aromatic substitution of 2,4‐dichloropyrimidines with N‐Boc protected 3 substituted oxindoles is reported. The reaction allows the formation of unsymmetrical all carbon quaternary centers in the benzylic position of heteroaromatic scaffolds and proceeds with high chemical yield and excellent func...

We present the thermolysis of cyclic hypervalent iodine(III) perfluoroalkyl transfer reagents carried out in standard GC-MS instrumentation. Through heating, these structures undergo fragmentation to afford perfluoroalkyl radicals F2n+1Cn* and each reagent can be characterized by means of a threshold temperature, TIP(n). This parameter TIP(n) not o...

A magnesium salt is capable of activating electrophilic hypervalent iodine reagents and thereby catalyzing the first direct trifluoromethylation of 3-substituted oxindoles. This synthetically important transformation leads to the formation of challenging perfluoroalkylated quaternary carbon centers under very mild reaction conditions and demonstrat...

Invited for the cover of this issue is Dmitry Katayev and co-workers from the group of Antonio Togni at the Swiss Federal Institute of Technology in Zürich. The image depicts a magnesium salt as a key player that is able to perform the direct electrophilic trifluoromethylation of 3-substituted oxindoles. Read the full text of the article at 10.1002...

The first example of a magnesium-catalyzed direct trifluoromethylation of 3-substituted oxindoles using an electrophilic hypervalent iodine reagent is reported. The reaction proceeds under unprecedented mild conditions leading to the formation of an all-carbon quaternary center in oxindoles in high chemical yield and demonstrates excellent function...

No abstract is available for this article.

Efficient protocols enabling the rapid installation of trifluoromethyl, as well as further functionalized fluoroalkyl groups by an electrophilic perfluoroalkylation of lactam-derived ketene silyl amides (KSAs) using hypervalent iodine reagents 1 and 2 have been developed.

An electrophilic trifluoromethylation of ketene silyl acetals (KSAs) by hypervalent iodine reagents 1 and 2 has been developed. The reaction proceeds under very mild conditions in the presence of a catalytic amount of trimethylsilyl bis(trifluoromethanesulfonyl)imide (up to 2.5 mol %) as a Lewis acid providing a direct access to a variety of second...

The Catalyst Review, now in its 28th year, continues to be an industry-leading publication designed to provide a global overview of events impacting the multi-billion dollar catalyst industry. The Catalyst Review offers both the immediacy and the continuity of key information critical to business strategy development, combining a global overview of...

A trimetallic palladium/copper/silver system has been developed that allows the decarboxylative Hiyama coupling of ortho-substituted aryl carboxylates with trialkoxyarylsilanes to give the corresponding biaryls. The cross-coupling is catalyzed by a Pd/N-heterocyclic carbene complex with silver carbonate aiding its reoxidation. Copper(II) fluoride a...

Two bulky, chiral, monodentate N-heterocyclic carbene ligands were applied to palladium-catalyzed asymmetric CH arylation to incorporate C(sp(3))H bond activation. Racemic mixtures of the carbamate starting materials underwent regiodivergent reactions to afford different trans-2,3-substituted indolines. Although this CArCalkyl coupling requires hig...

A rare, perfect case of a highly selective regiodivergent reaction of a racemic mixture is presented. Upon interaction with the Pd–(S,S)-NHC catalyst (NHC=N-heterocyclic carbene), the R enantiomer takes the right fork and the S enantiomer the left one. Thus, the racemic mixture reacts to give two regioisomeric enantiopure products. In this reaction...

Various (hetero)arenecarboxylic acids were converted to the corresponding Daugulis amides and nitrated selectively in the ortho-position in the presence of [CuNO3(PPh3)2] and AgNO2 at 50 °C. A microwave-assisted saponification allows regenerating the carboxylate group within minutes, which may then be removed tracelessly by protodecarboxylation, or...

Palladium complexes incorporating chiral N-heterocyclic carbene (NHC) ligands catalyze the asymmetric intramolecular α-arylation of amides producing 3,3-disubstituted oxindoles. Comprehensive DFT studies have been performed to gain insight into the mechanism of this transformation. Oxidative addition is shown to be rate-determining and reductive el...

What a couple! Arenes functionalized with donating groups undergo oxidative dehydrogenative coupling with alcohols in the presence of a copper/silver catalyst system. This intermolecular CH alkoxylation provides a convenient synthetic route to the important class of aryl ethers. The catalyst system also allows the alkoxylation of benzylic CH grou...

Advances in the efficient palladium–NHC catalysed synthesis of highly enantioenriched 2,3-trans-fused and 2-alkyl indolines via asymmetric C(sp3)–H activation of an unactivated methylene/methyl group are reported. Very high asymmetric inductions (up to 99% ee) were achieved at reaction temperatures ranging from 120 to 160 °C. Factors influencing th...

The biologically important heterocyclic system is readily available from substrates of type (I) and (III).

A palladium-catalyzed intramolecular α-arylation of an amide in the presence of a bulky chiral N-heterocyclic carbene ligand is the key step in the first catalytic synthesis of (3R)-6-chloro-3-(3-chlorobenzyl)-1,3-dihydro-3-(3-methoxyphenyl)-2H-indol-2-one ((R)-5). This oxindole, in racemic form, had been shown previously to be an anticancer agent....

A novel efficient NaOtBu-mediated protocol for the synthesis of 3,3-disubstituted aza-oxindoles proceeds via a Truce-Smiles rearrangement-cyclisation pathway.

Very high asymmetric inductions result in the Pd-catalyzed intramolecular arylation of amides to give 3,3-disubstituted oxindoles when new in situ-generated chiral N-hetero cyclic carbene (NHC*) ligands are employed. Structural studies show that conformational locking to minimize allylic strain is the key to understanding the function of these liga...

New sterically hindered chiral N-heterocyclic carbene (NHC) ligands were used in palladium catalysis to bring about a highly enantioselective C(sp3)-H activation on the methylene site of a cycloalkane moiety. The intramolecular coupling reaction of a prochiral N-aryl-N-cycloalkyl methyl carbamate required high temperatures (140–160 °C) and afforded...

N-Aryl, N-branched alkyl carbamates react with in situ generated chiral Pd-NHC catalysts by coupling a Pd-Ar moiety with an aliphatic C–H bond at high temperature to give enantioenriched 2-substituted and 2,3-disubstituted indolines. Prochiral precursors give single products with very high asymmetric induction. Chiral racemic precursors react in a...

A chiral palladium complex generated from N-heterocyclic carbene is successfully applied to the synthesis of highly enantioenriched trans-fused indolines.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

New Enders/Herrmann-type chiral N-heterocyclic carbene (NHC) ligands have been developed and applied in asymmetric palladium-catalyzed intramolecular alpha-arylations of amides. The best ligands feature the bulky tert-butyl group and ortho-substituted aryl groups at the stereogenic centers. Aryl bromides readily react at room temperature and aryl c...

Pd/PtBu(3)-catalysed intramolecular nucleophilic addition of aryl halides to alpha-ketoamides in the presence of nBuOH and base has been realized with high yields, providing a new, direct, and efficient synthetic strategy to obtain 3-hydroxyoxindoles.

A series of Co(III) anionic complexes of Schiff bases obtained from substituted salicylaldehydes and optically active amino acids has been synthesized. The ion pairing of these anions to a lithium cation can be used to induce asymmetry into lithium-catalyzed trimethylsilylcyanation of aldehydes and Michael reactions. The influence of the temperatur...

Chiral, coordinatively-saturated cobaltate(III) complexes of Schiff bases obtained from salicylaldehyde and the optically active amino acids, (S)-Val, (S)-Thr, and (S)-Trp, are formed as C2-symmetrical, octahedral, anionic Λ(S,S)-, and Δ(S,S)-diastereoisomeric complexes, which are easily separable by chromatography. The complexes are stereochemical...

Chiral dinuclear titanium(IV) complexes (generated in situ from hexadentate Schiff bases and titanium tetra-isopropoxide) have been found to be more effective catalysts for the asymmetric addition of trimethylsilyl cyanide to aldehydes and the ring opening of cyclohexene oxide than their mononuclear analogues. The best results were obtained for ben...

Chiral coordinatively saturated cobalt(III) complexes with Schiff bases of enantio-pure amino acids are formed as Λ and Δ-isomers, which are not transformed into each other under normal conditions. These complexes catalyze the formation of enantiomerically enriched cyanohydrins from aldehydes and Me3SiCN under homo-and heterogeneous catalysis.