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Introduction
C-H activation. Review writing
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Publications (416)
Expression of concern for ‘Nanocrystalline starch grafted palladium( ii ) complex for the Mizoroki–Heck reaction’ by Sanny Verma et al. , Dalton Trans. , 2013, 42 , 14454–14459, https://doi.org/10.1039/C3DT51685G.
The Pd-catalyzed inter- and intramolecular reactions of nitrogen compounds are often carried out with palladium carboxylates, sometimes in the presence of carboxylic acids or alkali metal carboxylates. This Mini-Review highlights the dependence of the reaction efficiency on the nature of the ligand and the carboxylate additives. The proposed reacti...
The efficiency of the formation of C−C bonds under palladium catalysis often depends on the nature of the carboxylate ligand and carboxylic acids or alkali metal carboxylates additives. This review which is Part C of a trilogy devoted to the topic, highlights the influence of the carboxylate units on domino diarylation and annelation reactions. The...
A variety of Pd‐catalyzed reactions are carried out with palladium carboxylates in the presence of carboxylic acids and/or alkali metal carboxylates. This review is Part A of three reviews highlighting the dependence of the efficiency of the formation of the different C−C bonds on the nature of the carboxylate unit. Part A concerns inter‐ and intra...
The efficiency of the formation of C−C bonds under palladium catalysis often depends on the nature of the carboxylate ligand and carboxylic acids or alkali metal carboxylates additives. This review which is Part B of a trilogy devoted to the topic, highlights the influence of the carboxylate unit on the hydro(hetero)arylation, hydroalkenylation and...
Transition-metal-catalyzed functionalization of traditionally unreactive carbon-hydrogen bonds offers an interesting tool for the organic synthesis. Moreover, arynes are highly reactive species intensively used as key intermediates for the synthesis of natural products. The two topics join up in this short review which covers the Pd- and Cu-catalyz...
A cheap, versatile and effective method of hornets elimination based on the contact of flying individuals with the 20-30% solution of NaOH is reported. Importantly, the insects survived from the contact with this basic solution transport the poison to the nest.
This review highlights the allylic C−H alkylation of alkenes (AAH) with nucleophiles under Pd⁰ or PdII catalysis and achiral or chiral conditions. The η³‐allylpalladium intermediates of these reactions are formed from the cleavage of an allylic hydrogen which becomes a leaving group, like the acetate moiety of allyl acetates during the classical Ts...
A surprising D12 symmetry inside-hive constructions of honey bees were disclosed. The well-established sensitivity of bees to the magnetic field led us to supposition that it may play a key role in steering of such regular architecture.
The Pd II -mediated cross-coupling of (hetero)arenes with alkenes may be an effective method for the formation of a C–C bond from two C–H bonds. This reaction was discovered by Fujiwara and his co-workers in 1967, which led to a number of reports that we first highlighted in 2011 (review with references till June 2010) and for which we retained the...
A rich array of reactions occur using N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc) as reactants, these two amides being able to deliver their own H, C, N, and O atoms for the synthesis of a variety of compounds. This account highlights the literature published since June 2018, completing previous reviews by the author.
Wacker-type reactions of terminal alkenes mainly lead to methyl ketones rather than aldehydes. The selective formation of aldehydes usually requires alkenes containing a suitable coordinating fragment. A few procedures however provide fair to high aldehyde/methyl ketone ratios in the absence of a directing group. This review, which is focused on th...
The cyclohexane oxidation by H2O2 using VO(acac)2 as starting catalyst in the presence of oxalic acid (OA) was studied. The dissociation of OA and VO(oxalate) formed in situ by interaction of VO(acac)2 with OA is the essence of the electrical conductance G elevation (or vice versa 1/G dropping). As follows from the electronic and cyclic voltammetry...
In a novel approach, an efficient non-enzymatic glucose sensor based on pure phase of aurivillius bismuth molybdate (BM or γ-Bi2MoO6) mixed metal oxides is reported. Three BM samples were synthesized, with/without l-cysteine (Cys) and dodecylamine (DDA) as additives, leading to different shapes: bullet (BM-C), confetti (BM-2Cys) and candy (BM-2DDA)...
Fascinating oscillations of color, kinetics of pH, cyclic voltammetry (CV) and UV‐vis spectra, ensued from supplementing of VO(acac)2‐acetonitrile solutions with micro‐amounts of H2O2, were greatly affected by the small additives of glyoxal and oxalic acid. Such effect was consisted in sufficient decreasing the sensitivity of samples by means of it...
DBU (1,8‐diazabicyclo[5.4.0]undec‐7‐ene) is traditionally considered to be a non‐nucleophilic base. Nevertheless, DBU possesses nucleophilic properties which mediate organic reactions and may lead to the formation of compounds containing the DBU scaffold. Participation of water to the processes affords there‐component products. The review covers th...
The Pd-mediated cross-coupling of (hetero)arenes with alkenes may be an effective method for the formation of a C–C bond from two C–H bonds. Discovered by Fujiwara and co-workers in 1967, this reaction led to a number of reports that we firstly highlighted in 2011 (review with references till June 2010) and for which, we retained the name “dehydrog...
The oxygenation of cyclohexane and toluene by O2 and H2O2 catalyzed by VO(acac)2 and Co(acac)2 was studied at 40–100 °C and 1–10 atm. Upon such conditions, the process can be remarkably (30× times) enhanced by the minute (6–15 mM) additives of oxalic acid (OxalH) or N-hydroxyphthalimide (NHPI). The revealed effect of OxalH on H2O2-piloted oxidation...
The exploitation of the ring strain of cyclopropanols, cyclobutanols and cyclobutenols has led to a variety of Pd-catalyzed reactions, especially when the ring is substituted with other functions. Cross-coupling and domino reactions have also been reported. The present review gathers together the literature results with special attention to the pro...
This review recounts the development by the authors of the Pd-catalyzed procedures devoted to various kinds of oxidation. Starting with reactions assisted with UV light, the research has explored reactions under light-free conditions: allylic oxidation, alcohol oxidation, etherification, Wacker oxidation and dehydrogenations with, always, accompany...
This review summarizes palladium-catalyzed carbonylation, transmetalation, and cross-coupling reactions that lead to carbonylated indoles from indoles and indolyl compounds. Special attention is drawn to procedures involving the C(sp2)–H substitution of free (NH)-indoles or (N-substituted)-indoles. Proposed mechanisms are described with, in some ca...
The dehydrogenation of carbonyl compounds to the corresponding α,β‐unsaturated carbonyl compounds, also known as the Saegusa reaction, is reviewed. Related methods involving enol acetates, alkyl enol ethers, allyl enol carbonates, allyl β‐keto carboxylates, allyl malonates, and α‐chloro ketones are also discussed.
The palladium‐catalyzed decarboxylative asymmetric protonation (DAP) of racemic allyl β‐keto esters using achiral protic species, first disclosed in 2006, is now a mature methodology for applications in asymmetric organic synthesis. In contrast, the mechanism of protonation remains unclear despite experimental and computational studies. The aim of...
N,N-Dimethylformamide and N,N-dimethylacetamide are multipurpose reagents which deliver their own H, C, N and O atoms for the synthesis of a variety of compounds under a number of different experimental conditions. The review mainly highlights the corresponding literature published over the last years.
Biomass or biomass derived compounds are ideal starting material for the synthesis of particularly functionalized platform chemicals. Thus furans such as hydroxymethylfurfural (HMR) or diformylfuran (DFF) are obtained from hexose containing biomass. Although possessing two reactive aldehyde functions, DFF was less frequently considered as a suitabl...
This review covers those domino reactions that involve, at least, both palladium‐catalyzed dehydrogenation of carbonyl compounds and Heck‐type reactions. While the former occurs under Pd(II) catalysis, a Pd(0) or Pd(II) catalyst is required for the latter, depending on the nature of the (hetero)arylating agent, ArX or ArH, respectively. Regeneratio...
This review summarizes Pd-catalyzed procedures leading to single C–O bonds from aliphatic C–H bonds of substrates bearing heteroatomic groups. Coordination of the latter to PdII species favors the activation of a C(sp³)–H bond and controls the regioselectivity, leading to a palladacycle as intermediate. Either PdII–Pd⁰ or PdII–PdIV redox catalytic...
A variety of chemical reactions are best carried out in N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc) than in other solvents. The interest of these polar solvents is not only their high dissolution power of various classes of substrates and their capacity to solvate anions. Moreover, these solvents can participate in dehydration, dehy...
The efficiency of the vanadyl(IV)acetylacetonate (1)–catalyzed oxidation of cyclohexane by hydrogen peroxide in acetonitrile increased in the presence of oxalic acid (2). The addition of 2 leads to the substitution of acac ligands by oxalate resulting in formation of vanadyl(IV)oxalate (3). That promotes the formation of cyclohexanol, cyclohexanone...
Starting from Diformylfuran (DFF) obtained from biomass, a new family of gemini surfactants has been synthesized. The polar group is composed of two amphoteric aminoacids attached to a tetrahydrofuran ring. During the preparation, the formation of metal salts is avoided in the final steps. At very low critical micelle concentrations (CMC) of around...
Biomass or biomass derived compounds are ideal starting material for the synthesis of particularly functionalized platform chemicals. Thus furans such as hydroxymethylfurfural (HMR) or diformylfuran (DFF) are obtained from hexose containing biomass. Although possessing two reactive aldehyde functions, DFF was less frequently considered as a suitabl...
Study the mild cyclohexane oxygenation using vanadyl(IV)acetylacetonate as the starting catalyst and H2O2 as the oxidant has shown that oxalic acid as activator alters the products ratio, increases yield and catalyst turnover number. According to the instrumental (ESI-MS, NMR, EPR, UV–vis, GC, pH, titrimetric) investigations both the parental VO(ac...
Celecoxib (CEL) as the very low water soluble drug was loaded 16 and 50% (w/w) through an impregnation method on varieties of alumina nanostructures such as synthetic sol-gel γ-alumina (Gam-Al), functionalized sol-gel γ-alumina (Gam-Al-NH2), organized nano porous alumina (Onp-Al) and then the results compared with commercial alumina (Com-Al) and SB...
This review summarizes the intermolecular PdII-catalyzed dehydrogenation procedures leading to regioselective coupling of alcohols with (hetero)arenes bearing tethered coordinating groups. Unusual oxidative conditions of catalyst regeneration are required, and the optimum oxidant varies with the substrate. Emphasis is placed on the mechanism of the...
A new derivative of dipodal 1,3-calix[4]arene-based chemosensor (R),which was containing several binding sites have been synthesized and characterized by NMR, IR and LC-MS spectroscopic methods. The selectivity of Rhas been investigated in aqueous methanol, resulting in fluorescence shift and selective recognition of Ag⁺ among 20 various alkali, al...
The title reaction proceeds with complete diastereoselectivity and high enantioselectivity through a kinetic resolution of the M-B-H adducts.
A rhodium‐catalyzed asymmetric synthesis of 5,5‐disubstituted cyclohexa‐1,3‐dienes has been achieved by [2+2+2] cycloaddition reactions between diynes and Morita–Baylis–Hillman (M‐B‐H) adducts as unsaturated substrates. Products containing two adjacent chiral centres (quaternary and tertiary, respectively) were obtained with complete diastereoselec...
This review covers the formation of Csp3-Csp3 bonds through Pd-catalyzed reactions of benzylic and heterobenzylic substrates bearing acetate, carbonate, phosphonate, or halide leaving groups, with malonate-type compounds, oxazoles, aldehydes, α,β-unsaturated aldehydes, oxindoles, or azlactones. Some of these coupling reactions have been carried out...
2,5-Diformylfuran (DFF) and 5-hydroxymethylfurfural (HMF) are interesting platform compounds in the chemical industry. A sustainable one-pot procedure is reported for the transformation of carbohydrates into DFF. Mono-, di- and polysaccharides as well as crude biomass (straw and bran) have been transformed. Depolymerisation, glucose isomerisation t...
The influence of calcination temperature (500, 600 and 700 °C) on NiO–MgO solid solution formation and the performance of the resulting catalysts in CO2 reforming of methane was studied. The solid solutions and resulting catalysts were characterized by Brunauer–Emmett–Teller, XRD, temperature-programmed reduction (TPR), TEM and thermal gravimetric...
This review covers Pd-catalyzed abstracting and borrowing hydrogen transfers from alcohols to C=C, C=O, and C=N bonds. An abstracting hydrogen transfer implies a reaction in which an alcohol serves only as a hydrogen atom source, whereas in a borrowing hydrogen transfer the alcohol is part of the final product. Both transfer types involve a palladi...
Palladium(II)-catalyzed procedures often use benzoquinone (BQ) to regenerate the catalyst. Besides its oxidation role, BQ can also promote various steps of the catalytic cycle. This review highlights the multifaceted properties of BQ and its analogues when involved in PdII-catalyzed oxidative reactions and presents mechanisms proposed in the litera...
Procédé de préparation de furane 2,5-dicarboxaldéhyde qui consiste à mettre en réaction le HMF ou un dérivé halogéné du HMF dans un solvant de la famille des sulfoxydes à une température comprise entre 50 et 200 DEG C pendant une durée comprise entre 1 et 36 heures.
4,5-Diazafluorenone was found to promote the dehydrogenative Heck reaction of furans and thiophenes with hindered alkenes. High stereoselectivity was achieved in the synthesis of β,β-diaryl α,β-unsaturated alkenes. A mechanism, based on ESI-MS studies, kinetic experiments, and competitive reactions, was proposed. The ligand influences C–H bond acti...
Oxidation of starch under Fenton conditions leads to a mixture of acids having Ca sequestering properties. The efficiency of the process increases under visible light irradiation; this is mainly due to the improvement of the depolymerization of the substrate. Whatever the experimental conditions, that is Fenton or photo-Fenton, the oxidation produc...
This review covers the palladium-catalyzed annelations of internal alkynes through reactions leading to the loss of only two hydrogens from the substrates. They occur via (i) dual C–H bond activation, (ii) both C–H and N–H bond activation, (iii) successive amino(or oxy)palladation and C–H bond activation, or (iv) C–H bond activation followed by a H...
Dehydration of monoaldoses and aldoketoses under catalyst-free conditions has been studied varying the solvent nature, the concentration and the heating mode (conventional or microwaves). Best results were obtained in dimethylsulfoxide (DMSO) indicating that DMSO has a dual role: solvent and reaction mediator. Thus, d-fructose provided 5-hydroxymet...
Optically active 2-substituted-1-indanones or 2-substituted-1-tetraiones are isolated from amino alcohol-mediated asymmetric domino reactions of alpha-disubstituted ketones, beta-ketoesters, enol carbonates, alpha, beta-unsaturated ketones, a silyl enol ether, or a beta-ketoacid, with some of these reactions occurring under UV-light irradiation or...
2,5-Diformylfuran (DFF) was obtained by heating a solution of 5-(hydroxymethyl)furfural in DMSO. The addition of acids or salts improved the selectivity, especially if bromides were employed. Good yields of DFF were obtained with HBr or NaBr as the catalyst. One-pot procedures were developed from fructose, which led to DFF in medium yields. This tr...
The Pd-catalysed formation of a C-O bond from allenes mainly occurs via the inter- or intramolecular reaction with a hydroxyl group belonging to an alcohol, a phenol or an acid. A carbonyl or a carbonate entity can also be involved. In most cases, the formation of the C-O bond is one step of a domino reaction leading also to a C-C or C-N bond, or t...
This chapter mainly concerns the use, in dimethyl sulfoxide (DMSO), of catalytic amounts of palladium acetate to carry out the aerobic oxidation of allylic and benzylic alcohols, the mechanistic studies of this process, and the comparison of the method efficiency with the previous Pd-catalyzed aerobic alcohol oxidations. Although the mechanism is n...
The metal-free stoichiometric click reaction between thiol-functionalized nanocrystalline starch and yne-functional oxo-vanadium Schiff base has been demonstrated to be a simple, quantitative, mild and efficient approach for the development of heterogenized homogeneous complex via covalent bonding. The developed catalyst has found to be highly effi...
Sulfoxides and sulfones as solvents have been used for the glycosidation of various carbohydrates with decanol in the absence of an added catalyst. The production of decyl-D-xylosides has been studied in dimethylsulfoxide and the importance of parameters such as pressure and temperature on the reaction time has been pointed out. Organic acids produ...
Nanocrystalline starch produced from the acid hydrolysis of gelatinized starch has been used for the first time to support palladium(ii) ethylenediamine complex. The nanocrystalline starch supported Pd(ii) complex was found to be an efficient and efficiently recycled catalyst for the Mizoroki-Heck reaction of furans and thiophenes with styrenes und...
Jacques Muzart was born in 1946, in Vienne la Ville, a small village in the Argonne area, 200 km east of Paris. He studied chemistry at the Université de Champagne-Ardenne and received his degrees (Doctorat de 3ème cycle in 1972, Doctorat d'Etat in 1976) for his work with J.-P. Pète on photochemical rearrangements of α,β-epoxyketones and β-diketone...
A method for preparing ketose sugars, characterised in that: 1/ at least one aldose sugar or a solution or a suspension of said sugar in water is solubilised, in at least one organic solvent; 2/ the organic solution obtained is brought into contact with a catalyst, in order to convert the aldose into ketose by means of an isomerisation reaction; 3/...
The formation of 2-methyl-1-tetralone from the metal-free and
base-free decarboxylation of 2-methyl-1-tetralone-2-carboxylic
acid involves 2-methyl-3,4-dihydro-1-naphthol as an intermediate.
The reaction of this enol with atmospheric oxygen leads to
2-hydroperoxy-2-methyl-1-tetralone. The oxidation mechanism is
confirmed by quantum chemical calcula...
The aerobic dehydrogenative Heck reaction (DHR) of heterocycles with styrenes was found to be more efficient in the absence of metallic co‐oxidants. According to a study of the isotope effect, the CH cleavage was the rate‐determining step of the catalytic cycle. Electrospray ionization mass spectrometry, subsequent MS/MS, and high‐resolution mass s...
In the presence of alcohols and a very low amount of the aluminium dodecaphosphotungstate AlPW O , styrene oxide efficiently leads to -alkoxy alcohols at low temperatures. 12 40
The intermolecular coupling of aryl or vinyl halides (or pseudohalides) with linear alkenes having an allylic or homoallylic heteroatomic substituent occurs under palladium-catalyzed conditions. The 1,2-insertion of the aryl- or vinylpalladium intermediate into the double bond is followed by the elimination of either a hydride or the heteroatomic s...
Jean Le Bras Jean Le Bras was born in Brest and obtained his Engineering Diploma from ENSCP-Paris and his M.Sc. degree (DEA) from Université Pierre et Marie Curie. In 1996, he joined the group of Dr. Hani Amouri where he studied iridium mediated phenols functionalization and obtained his Ph.D. in 1998. He then joined the group of Professor John A....
Electrospray ionization mass spectrometry, subsequent MS/MS, and high-resolution mass spectrometry were used to study the dehydrogenative Heck reaction of 2-alkylfurans 1 with acrylates 2, using [Pd(OAc)(2)](3) as the precatalyst, benzoquinone (BQ) as the stoichiometric oxidant, and a mixture of DMSO and AcOH as the solvent. Complexation of [Pd(OAc...
Furans and thiophenes undergo C—H activation with Pd(OAc)2 to give a series of coupling products with styrenes.
![Fig. 4 ESI(2)-MS/MS (6-8 eV) of [Pd 2 Cl 5 (1e)] 2 and [Pd 2 Cl 5 (2e)] 2 .](profile/Jacques-Muzart/publication/255763480/figure/fig6/AS:667689135665156@1536200903319/ESI2-MS-MS-6-8-eV-of-Pd-2-Cl-5-1e-2-and-Pd-2-Cl-5-2e-2_Q320.jpg)
![Fig. 5 ESI(2)-MS/MS (15-20 eV) of [Pd 2 Cl 4 (1e-H)] 2 and [Pd 2 Cl 4...](profile/Jacques-Muzart/publication/255763480/figure/fig7/AS:667689135661064@1536200903333/ESI2-MS-MS-15-20-eV-of-Pd-2-Cl-4-1e-H-2-and-Pd-2-Cl-4-2e-H-2_Q320.jpg)
The monitoring, by ESI-MS, of the Wacker oxidation of alkenes, using benzoquinone as terminal oxidant, has shown that dinuclear palladium complexes are more involved as active catalytic intermediates than mononuclear species. Kinetic experiments have confirmed a palladium-dependency greater than first-order, pointing out that the catalytic active s...
This review is dedicated to hemicelluloses and its main component D-xylose as raw materials for the surfactant industry. The context of D-xylose or of the D-xylose containing polysaccharides uses in the industry is first considered and the straightforward preparation of pentose based surfactants, their properties, and their situation in the field o...
In the presence of catalytic amounts of a Keggin (H(3)PW(12)O(40)), Wells-Dawson (H(6)P(2)W(18)O(62)) or Preyssler (H(14)NaP(5)W(30)O(110)) heteropolyacid, alpha-methylstyrene (1) leads to dimers. The efficiency and the selectivity toward 2,4-diphenyl-4-methyl-1-pentene (2), 2,4-diphenyl-4-methyl-2-pentene (3) and 1,1,3-trimethyl-3-phenylindan (4)...
This short review examines the palladium-catalyzed arylation of the C=C bond of Baylis-Hillman adducts. It summarizes the different intermolecular and intramolecular reaction procedures, and contains detailed tables making it easier to compare their efficiency.
1 Introduction
2 Intermolecular Reactions
2.1 Without Decarboxylation
2.2 With Decarboxy...
This review surveys the different Pd-catalyzed procedures leading to the oxidation of the C C bonds. The reactivity and selectivity depend on the substitution of the triple bond, 1,2-diarylethynes being the most reactive. The main oxidation product, an 1,2-diketone, an ester or a furan, depends on both the used procedure and the substrate. Plausibl...
Vanadyl(IV)-acetylacetonate-catalyzed oxidation of cyclohexane with H(2)O(2), at 40 degrees C under air atmosphere, has been studied in the presence of small quantities of oxalic acid. The process efficiency is increased by this additive and depends on the nature of the solvent (MeCN >= MeOH > Me(2)CO >= 2-PrOH > EtOH). The relationships between th...
Intermolecular phosphine-free Heck reactions occur in high yields, under basic conditions, using a catalytic mixture of Pd(OAc)2 and a β-amino alcohol. It is assumed that the active catalytic species are N-liganded Pd0 species. The recent mechanistic proposal, from Petrović et al., concerning Heck reactions catalyzed with PdCl2[NH(CH2CH2OH)2]2 is c...
This review surveys a range of reactions in aqueous media mainly performed from the authors team, some of the results being only disclosed in PhD thesis. Hydrophilic ligands, [(HOCH2CH2NHCOCH2)2NCH2]2 or L-proline, have been used to carry out Cucatalyzedallylic benzoyloxylations and Pd-catalyzed allylic alkylations, isomerizations, telomerizations...
This review highlights the different reactions of epoxides induced by stoichiometric or catalytic amounts of palladium, except for hydrogenolysis procedures and reactions involving additions to alpha,beta-unsaturated epoxides. The proposed mechanisms are described, with some personal observations in some cases.
Intermolecular dehydrogenative Heck reaction (DHR), leading to the formation of a C-C bond from two C-H bonds, is discussed. For the stoichiometric DHRs carried out in AcOH or in solvent mixtures containing AcOH, it is found that AcOH could act as an ionizing agent protoning off an acetate ligand to afford [ArPd(II)]+ species. Studies on the Mizoro...
This review surveys the different Pd-catalyzed procedures leading to the oxidation of the CC bonds. The reactivity and selectivity depend on the substitution of the triple bond, 1,2-diarylethynes being the most reactive. The main oxidation product, an 1,2-diketone, an ester or a furan, depends on both the used procedure and the substrate. Plausible...
Questions
Question (1)
I read with attention your paper reported in Org. Lett. in 2018 (p. 7015). You wrote “In comparison with conditions A, comparable or better yields were achieved under conditions B for most products (Schemes 2 and 3)”. According to the results of Schemes 2 and 3, it appears that the best yields are usually obtained using Procedure A. Could you give me explanations?
