Direct Amination of Benzene with Ammonia by Flow Plasma Chemistry.

Amine derivatives, including aniline and allylic amines, can be formed in a single-step process from benzene and an ammonia plasma in a microreactor. Different process parameters such as temperature, residence time, and plasma power were evaluated to improve the reaction yield and its selectivity toward aminated products and avoid hydrogenated or oligomerized products. In parallel, simulation studies of the process have been carried out to propose a global mechanism and gain a better understanding of the influence of the different process parameters. The exploration of diverse related alkenes showed that the double bonds, conjugation, and aromatization influenced the amination mechanism. Benzene was the best reactant for amination based on the lifetime of radical intermediates. Under optimized conditions, benzene was aminated in the absence of catalyst with a yield of 3.8 % and a selectivity of 49 % in various amino compounds.

Regime Switch in the Dual-Catalyzed Coupling of Alkyl Silicates with Aryl Bromides.

Metallaphotoredox catalyzed cross-coupling of an arylbromide (Ar-Br) with an alkyl bis(catecholato)silicate (R-Si⊖ ) has been analyzed in depth using a continuum of analytical techniques (EPR, fluorine NMR, electrochemistry, photophysics) and modeling (micro-kinetics and DFT calculations). These studies converged on the impact of four control parameters consisting in the initial concentrations of the iridium photocatalyst ([Ir]0 ), nickel precatalyst ([Ni]0 ) and silicate ([R-Si⊖ ]0 ) as well as light intensity I0 for an efficient reaction between Ar-Br and R-Si⊖ . More precisely, two regimes were found to be possibly at play. The first one relies on an equimolar consumption of Ar-Br with R-Si⊖ smoothly leading to Ar-R, with no side-product from R-Si⊖ and a second one in which R-Si⊖ is simultaneously coupled to Ar-Br and degraded to R-H. This integrative approach could serve as a case study for the investigation of other metallaphotoredox catalysis manifolds of synthetic significance.

N-Heterocyclic Carbene Boranes: Dual Reagents for the Synthesis of Gold Nanoparticles.

N-Heterocyclic carbenes (NHCs) have drawn considerable interest in the field of nanomaterials chemistry as highly stabilizing ligands enabling the formation of strong and covalent carbon-metal bonds. Applied to gold nanoparticles synthesis, the most common strategy consists of the reduction of a preformed NHC-AuI complex with a large excess of a reducing agent that makes the particle size difficult to control. In this paper, we report the straightforward synthesis of NHC-coated gold nanoparticles (NHC-AuNPs) by treating a commercially available gold(I) precursor with an easy-to-synthesize NHC-BH3 reagent. The latter acts as both the reducing agent and the source of surface ligands operating under mild conditions. Mechanistic studies including NMR spectroscopy and mass spectrometry demonstrate that the reduction of gold(I) generates NHC-BH2 Cl as a by-product. This strategy gives efficient control over the nucleation and growth of gold particles by varying the NHC-borane/gold(I) ratio, allowing unparalleled particle size variation over the range of 4.9±0.9 to 10.0±2.7 nm. Our strategy also allows an unprecedented precise and controlled seeded growth of gold nanoparticles. In addition, the as-prepared NHC-AuNPs exhibit narrow size distributions without the need for extensive purification or size-selectivity techniques, and are stable over months.

Gold-Catalyzed Addition of Propargyl Acetates to Olefins via O-Acyl Migration/Cyclopropanation Sequence: Insight into the Diastereoselective Formation of the Alkene.

This article discloses a study on the well-known addition of propargyl acetates to olefins via an O-acyl migration/cyclopropanation sequence. Herein, we show that the stereochemical outcome of the olefin is strongly dependent on the gold catalyst and reaction parameters (concentration, temperature, and alkene partner equivalents); the E- and Z-isomers can be selectively formed by the judicious choice of reaction conditions.

Boron, silicon, nitrogen and sulfur-based contemporary precursors for the generation of alkyl radicals by single electron transfer and their synthetic utilization.

Recent developments in the use of boron, silicon, nitrogen and sulfur derivatives in single-electron transfer reactions for the generation of alkyl radicals are described. Photoredox catalyzed, electrochemistry promoted or thermally-induced oxidative and reductive processes are discussed highlighting their synthetic scope and discussing their mechanistic pathways.

Organopotassium-Catalyzed Silylation of Benzylic C(sp3 )-H Bonds.

Benzylsilanes have found increasing applications in organic synthesis as bench-stable synthetic intermediates, yet are mostly produced by stoichiometric procedures. Catalytic alternatives based on the atom-economical silylation of benzylic C(sp3 )-H bonds remain scarcely available as specialized directing groups and catalytic systems are needed to outcompete the kinetically-favored silylation of C(sp2 )-H bonds. Herein, we describe the first general and catalytic-in-metal undirected silylation of benzylic C(sp3 )-H bonds under ambient, transition metal-free conditions using stable tert-butyl-substituted silyldiazenes (tBu-N=N-SiR3 ) as silicon source. The high activity and selectivity of the catalytic system, exemplified by the preparation of various mono- or gem-bis benzyl(di)silanes, originates from the facile generation of organopotassium reagents, including tert-butylpotassium.

Organometallic catalysis under visible light activation: benefits and preliminary rationales.

Organometallic catalysis under visible light activation is an emerging field. Activation by photosensitization or by direct light absorption of organometallic complexes can facilitate or trigger elementary steps in a catalytic cycle such as pre-catalyst reduction, oxidative addition, transmetalation and reductive elimination, as well as the ability of generating radical intermediates, widening the structural diversity offered by classical couplings. This perspective aims to highlight key examples of these light-induced or enhanced processes, with an emphasis on the underlying mechanisms involved.

Synthesis and Reactivity of Martin's Spirosilane-Derived Chloromethylsilicate.

Pentacoordinate silicon derivatives with a chloromethyl ligand are versatile compounds that are usually obtained from the corresponding tetravalent trialkoxy- or trihalogeno(chloromethyl)silane. We describe herein the synthesis of a chloromethylsilicate bearing two Martin's ligands readily obtained by addition of in situ generated chloromethyllithium to a spirosilane. The reactivity of this new species was evaluated and it has been established that the chloride is displaced by strong nucleophiles such as alkyllithiums and (hetero)aryllithiums. In Lewis acidic conditions, the pentacoordinate silicon species rearranges through a formal insertion of a methylene into one Si-C bond, to form a new tetravalent spirosilane with a six-membered ring. The same kind of rearrangement can be triggered also by addition of a Lewis base. The mechanism of the rearrangement in both conditions has been studied by means of DFT calculations.

Synthesis and Optical Resolution of Configurationally Stable Zwitterionic Pentacoordinate Silicon Derivatives.

Stereogenic silicon centres in functionalised tetracoordinated organosilanes generally exhibit very high configurational stability under neutral conditions. This stability drops completely when higher coordination states of the silicon centre are reached due to rapid substituent exchange. Herein we describe the synthesis of chiral and neutral pentacoordinate silicon derivatives with high configurational stability. The zwitterionic nature of these air- and water-tolerant species allows for the first time their direct and efficient optical resolution using chiral HPLC techniques. By means of this method, pentacoordinate silicon compounds exhibiting high Si-inversion have been obtained as single enantiomers. A rationalisation of the enantiomerisation pathways has been also carried out using DFT calculations.

Phenyl Silicates with Substituted Catecholate Ligands: Synthesis, Structural Studies and Reactivity.

While the generation of aryl radicals by photoredox catalysis under reductive conditions is well documented, it has remained challenging under an oxidative pathway. Because of the easy photo-oxidation of alkyl bis-catecholato silicates, a general study of phenyl silicates bearing substituted catecholate ligands has been achieved. The newly synthesized phenyl silicates have been fully characterized, and their reactivity has been explored. It was found that, thanks to the substitution of the catecholate moiety, notably with the 4-cyanocatecholato ligand, the phenyl radical could be generated and trapped. Computational studies provided a rationale for these findings.

A Parisian Vision of the Chemistry of Hypercoordinated Silicon Derivatives.

Less than ten years of acquaintance with hypercoordinated silicon derivatives in our lab is described in this account. Martin's spirosilane derivatives open new opportunities as ligands and as agents for the activation of small molecules and bis-catecholato silicates have proven to be exquisite radical precursors in photoredox conditions for broad synthetic applications.

Iron and cobalt catalysis: new perspectives in synthetic radical chemistry.

This review deals with some key synthetic developments based on the use of iron or cobalt complexes to promote radical reactivity which have been devised over the last decades. We have more particularly focused on reactions for which the impact of this chemistry has yielded greener alternatives to existing processes and also on new transformations, notably hydrogen atom transfer (HAT) triggered processes, which can be promoted through the use of metallic complexes. Preliminary synthetic developments based on the use of photoactive iron and cobalt complexes are also covered.

Indolizy Carbene Ligand. Evaluation of Electronic Properties and Applications in Asymmetric Gold(I) Catalysis.

We report herein a new family of carbene ligands based on an indolizine-ylidene (Indolizy) moiety. The corresponding gold(I) complexes are easily obtained from the gold(I)-promoted cyclization of allenylpyridine precursors. Evaluation of the electronic properties by experimental methods and also by DFT calculations confirms strong σ-donating and π-accepting properties of these ligands. Cationization of the gold(I) complexes generates catalytic species that trigger diverse reactions of (poly)unsaturated precursors. When armed with a methylene phosphine oxide moiety on the stereogenic center adjacent to the nitrogen atom, the corresponding bifunctional carbene ligands give rise to highly enantioselective heterocyclizations. DFT calculations brought some rationalization and highlighted the critical roles played by the phosphine oxide group and the tosylate anion in the asymmetric cyclization of γ-allenols.

Permethylated NHC-Capped α- and ß-Cyclodextrins (ICyDMe ) Regioselective and Enantioselective Gold-Catalysis in Pure Water.

A series of water-soluble encapsulated copper(I), silver(I) or gold(I) complexes based on NHC-capped permethylated cyclodextrins (ICyDMe ) were developed and used as catalysts in pure water for hydration, lactonization, hydroarylation and cycloisomerization reactions. ICyDMe ligands gave cavity-based high regioselectivity in hydroarylations, and high enantioselectivities in gold-catalyzed cycloisomerizations reactions giving up to 98 % ee in water. These ICyDMe are therefore useful ligands for selective catalysis in pure water.

Interaction between Spirosilanes and Lewis Bases: from Coordination to Frustration.

In this work, the interaction between Lewis bases, especially N-heterocyclic carbenes (NHCs), and hindered neutral silicon derivatives featuring high Lewis acidity is described. The formation of normal and abnormal Lewis adducts could be controlled by varying the acidity of the corresponding tetravalent spiro organosilane. Some DFT calculations permitted to gain insight into the thermodynamics of the NHC-spirosilane interaction featuring various NHCs differing in size and σ-donor capacity. Spirosilanes are introduced as new Lewis partners in frustrated Lewis pair (FLP) chemistry and some FLP-type reactivities are presented, in particular the activation of formaldehyde that could occur with both hindered NHCs and phosphines.

Direct Synthesis of N-Heterocyclic Carbene-Stabilized Copper Nanoparticles from an N-Heterocyclic Carbene-Borane.

N-Heterocyclic carbene (NHC)-stabilized copper nanoparticles (NPs) were synthesized from an NHC-borane adduct and mesitylcopper(I) under thermal conditions (refluxing toluene for 2.5 h). NPs with a size distribution of 11.6±1.8 nm were obtained. The interaction between Cu NPs and NHC ligands was probed by X-ray photoelectron spectroscopy, which showed covalent binding of the NHC to the surface of the NPs. Mechanistic studies suggested that NHC-borane plays two roles: contributing to the reduction of [CuMes]2 to release Cu0 species and providing NHC ligands to stabilize the copper NPs.

Carbonylation of Alkyl Radicals Derived from Organosilicates through Visible-Light Photoredox Catalysis.

Primary, secondary, and tertiary alkyl radicals formed by the photocatalyzed oxidation of organosilicates underwent efficient carbonylation with carbon monoxide (CO) to give a variety of unsymmetrical ketones. This study introduces the possibility of radical carbonylation under a photooxidative regime.

Copper-Catalyzed Aziridination with Redox-Active Ligands: Molecular Spin Catalysis.

Small-molecule catalysts as mimics of biological systems illustrate the chemists' attempts at emulating the tantalizing abilities displayed by nature's metalloenzymes. Among these innate behaviors, spin multistate reactivity is used by biological systems as it offers thermodynamic leverage towards challenging chemical reactivity but this concept is difficult to translate into the realm of synthetic organometallic catalysis. Here, we report a rare example of molecular spin catalysis involving multistate reactivity in a small-molecule biomimetic copper catalyst applied to aziridination. This behavior is supported by spin state flexibility enabled by the redox-active ligand.

Photoredox Catalysis for the Generation of Carbon Centered Radicals.

Radical chemistry has witnessed over the last decades important advances that have positioned it as a methodology of choice in synthetic chemistry. A number of great attributes such as specific reactivities, the knowledge of the kinetics of most elementary processes, the functional group tolerance, and the possibility to operate cascade sequences are clearly responsible for this craze. Nevertheless, at the end of the last century, radical chemistry appeared plagued by several hurdles to overcome such as the use of environmentally problematic mediators or the impossibility of scale up. While the concept of photocatalysis was firmly established in the coordination chemistry community, its diffusion in organic synthetic chemistry remained sporadic for decades until the end of the 2000s with the breakthrough merging of organocatalysis and photocatalysis by the MacMillan group and contemporary reports by the groups of Yoon and Stephenson. Since then, photoredox catalysis has enjoyed particularly active and intense developments. It is now the topic of a still increasing number of publications featuring various applications from asymmetric synthesis, total synthesis of natural products, and polymerization to process (flow) chemistry. In this Account, we survey our own efforts in this domain, focusing on the elaboration of new photocatalytic pathways that could lead to the efficient generation of C-centered functionalized alkyl and aryl radicals. Both reductive and oxidative manifolds are accessible through photoredox catalysis, which has guided us along these lines in our projects. Thus, we studied the photocatalytic reduction of onium salts such as sulfoniums and iodoniums for the production of the elusive aryl radical intermediates. Progressing to more relevant chemistry for synthesis, we examined the cleavage of C-O and the C-Br bonds for the generation of alkyl C-centered radicals. Activated epoxides could serve as valuable substrates of a photocatalyzed variant of the Nugent-RajanBabu-Gansäuer homolytic cleavage of epoxides. Using imidazole based carbamates, we could also devise the first photocatalyzed Barton-McCombie deoxygenation reaction. Finally, bromophenylacetate can be reduced using the [Au2(µ-dppm)2]Cl2 photocatalyst under UVA or visible-light. This was used for the initiation of the controlled atom transfer radical polymerization of methacrylates and acrylates in solution or laminate. Our next endeavors concerned the photocatalyzed oxidation of stabilized carbanions such as enolates of 1,3-dicarbonyl substrates, trifluoroborates, and more extensively bis-catecholato silicates. Because of their low oxidation potentials, the later have proved to be exquisite sources of radical entities, which can be engaged in diverse intermolecular reactions such as vinylation, alkynylation, and conjugate additions. The bis-catecholato silicates were also shown to behave as excellent partners of dual photoredox-nickel catalysis leading in an expeditious manner to libraries of cross coupling products.

Circumventing Intrinsic Metal Reactivity: Radical Generation with Redox-Active Ligands.

Nickel complexes have gained sustained attention as efficient catalysts in cross-coupling reactions and co-catalysts in dual systems due to their ability to react with radical species. Central to this reactivity is nickel's propensity to shuttle through several accessible redox states from Ni0 to NiIV . Here, we report the catalytic generation of trifluoromethyl radicals from a nickel complex bearing redox-active iminosemiquinone ligands. This unprecedented reactivity is enabled through ligand-based oxidation performing electron transfer to an electrophilic CF3+ source while the nickel oxidation state is preserved. Additionally, extension of this reactivity to a copper complex bearing a single redox equivalent is reported, thus providing a unified reactivity scheme. These results open new pathways in radical chemistry with redox-active ligands.