Hervé Clavier

Hervé Clavier
Aix-Marseille Université | AMU · Institut des Sciences Moléculaires de Marseille (UMR 7313 ISM2)

PhD

About

102
Publications
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Publications

Publications (102)
Article
A rhodium(III)-based catalytic system has been used to develop a C-H bond activation of benzaldehyde derivatives and subsequent functionalization with dioxazolones in order to afford imides. The importance of the nature of the directing group to perform selectively the aldehydic C-H bond activation has been highlighted. The scope investigation show...
Article
From achiral imidazolinium salts, chiral transition metal complexes containing an N‐heterocyclic carbene (NHC) ligand were prepared (metal = palladium, copper, silver, gold, rhodium). Axial chirality in these complexes results from the formation of the metal‐carbene bond leading to the restriction of rotation of dissymmetric N‐aryl substituents abo...
Article
Series of chiral palladium(II) allyl and cinnamyl complexes bearing a C1‐symmetric N‐heterocyclic carbenes were synthesized from achiral precursors. The chirality of theses complexes results from the formation of the carbene‐palladium bond which restricts the rotation of dissymmetric N‐aryl substituents of the NHC and thus creates an axis of chiral...
Article
In a previous work, the ability of gold-carbonyl bond dissociation energies (BDEs) to describe ligand effects in gold(I) complexes was probed using collision-induced dissociation measurements. Despite the large experimental error of the technique, results agreed with theoretical description of these effects. We propose here another experimental app...
Article
Transition metal‐catalyzed hydroalkynylation reactions are efficient transformations allowing the straightforward formation of functionalized alkynes. Therein, we disclose the cobalt‐catalyzed hydroalkynylation of vinylaziridines giving rise to both linear and branched enynes. The optimization of the reaction conditions allowed to determine the key...
Article
2-Substituted 1,3-indandione derivatives are known to undergo a photochemical rearrangement into phthalides. We find that in the presence of a substituent involving a double carbon-carbon bond in the vicinity of the carbonyl group in spiro-1,3-indandiones, a variety of other types of intramolecular photochemical reactions readily occur: 1,3-acyl sh...
Article
Well-defined optically pure Transition Metal-complexes bearing C1- and C2-symmetric N- Heterocyclic Carbene (NHC) ligands were prepared from prochiral NHC precursors. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces an axis of chirality. Configurationally stable atropisomers of variou...
Preprint
Well-defined optically pure copper-complexes are obtained from prochiral N- Heterocyclic Carbene (NHC) ligands. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces axial chirality. Configurationally stable (Sa)- and (Ra)-atropisomers of various Cu-complexes are isolated by preparative ch...
Article
Full-text available
Ligand electronic effects in gold(I) chemistry have been evaluated by means of the experimental determination of M-CO bond dissociation energies for 16 [L-Au-CO]+ complexes, bearing L ligands widely used in gold catalysis. Energy-resolved analyzes have been achieved using tandem mass spectrometry with collision induced dissociation. Coupled to DFT...
Article
A cobalt-catalysed C-H allylation of aromatic and hetereoaromatic compounds with vinylaziridines is described. This transformation occuring under mild reaction conditions proceeds through C-H activation, carbon-carbon double insertion and β-nitrogen elimination....
Article
Having previously established that 1,3-diones could be used as nucleophiles to perform additions to ynamides, highly selective hydroalkoxylation of internal ynamides is now described herein. Several catalytic systems were compared to carry out this transformation including transition metal-based catalysts or Lewis acids. ZnI2 was found to be both v...
Article
The intramolecular [4+2] cycloadditions of dienynes was investigated using cobalt-based catalysts. Substrates without substitution on alkyne moiety were found to react under thermal activation. The use of a cobalt salt as catalyst made reactions cleaner by limiting the formation of byproducts. Cycloadditions with dienynes possessing a substituent o...
Article
Proazaphosphatranes, also known as Verkade's superbases, have been investigated as ligands for gold(I). If the coordination to the gold center by the phosphorus atom suggests a phosphine-like behavior, gold(I)-containing Verkade's superbase complexes could be also prepared from the weak conjugated acid azaphosphatrane by the formation of the corres...
Article
Metal-phosphinito-phosphinous acid complexes are interesting catalysts exhibiting unique reactivities. In this account, we intend to provide a clear overview of palladium- and platinum-phosphinito-phosphinous acid complexes, their preparation from secondary phosphine oxides, and their applications in catalysis. They have been mainly used to develop...
Article
Palladium(II) acetate in association with secondary phosphine oxides provides an efficient catalytic system for [2+1] cycloadditions starting from oxanorbornene derivatives and tertiary propargyl esters giving rise to vinylidenecyclopropanes.
Article
Full-text available
A series of [RuCl2(η(6)-p-cymene)] complexes bearing phosphinous acid (PA) ligands have been straightforwardly prepared from the dimer [RuCl2(p-cymene)]2 and secondary phosphine oxides (SPOs) and fully characterized. The steric parameter quantification of PAs, other L ligands and η(6)-p-cymene allowed a better comprehension of the coordination chem...
Article
Palladium(II) acetate in association with secondary phosphine oxides provides an efficient catalytic system for [2+1] cycloadditions starting from oxanorbornene derivatives and tertiary propargyl esters giving rise to vinylidenecyclopropanes. This reaction is specific to bidentate phosphinito–phosphinous acid ligands generated from secondary phosph...
Article
The Cover shows how the phosphinous acid–phosphinito catalyst (PAP-Cat, top-left of the picture) and the Herrmann–Beller catalysts (H-B, bottom-right) give rise to chemodivergent processes. In their Full Paper, P. Nava et al. combine experimental and computational approaches to understand the versatile role of the ligands. They show that PAP-Cat ca...
Article
Whereas the reaction of norbornadiene with terminal alkynes in the presence of a phosphapalladacycle catalyst leads to the formation of hydroalkynation products, the use of phosphinous acid-phosphinito-containing palladium complexes gives rise to formal [2+1] cycloadducts. An experimental and computational approach was employed to study the mechani...
Article
We disclosed therein a new reaction of reductive isomerization methylenecyclopropanes (MCPs) to vinylcyclopropanes (VCPs). On treatment with sodium metal in liquid ammonia, MCPs bearing a C-O bond at allylic position undergo both a reductive cleavage of the C-O bond and an isomerization of the C-C double bond giving rise to VCPs. The scope of the r...
Article
Two series of ruthenium carbonyl complexes bearing either one secondary phosphine oxide ligand or two phosphinous acids have been synthesized and characterized. The catalytic behavior of these complexes has been then investigated for the cycloisomerization of arenynes. This study highlighted a strong relationship between ligands’ and substrates’ su...
Chapter
The generation of medium-sized rings possessing defined constitutions and configurations is an important and challenging goal in organic synthesis. The key factors favoring the cyclization versus polymerization concern structural features, length of chain(s), nature of atoms in chains, as well as concentration of reaction media. This chapter discus...
Article
A new metal-catalyzed addition reaction of 1,3-diketones to ynamides, which provides access to unprecedented alkoxy-substituted enamides, is disclosed herein. A screening of catalytic systems showed that both a phosphapalladacycle and a cationic gold complex were capable of promoting this reaction rapidly and cleanly. The scope investigation reveal...
Article
A series of new secondary phosphine oxide (SPO)–gold(I) complexes have been synthesized and characterized by X-ray crystallography. Complexes exhibited dimeric structures interconnected by O–H···Cl hydrogen bonds. Their first use in homogeneous catalysis is reported and suggests a broad field of application in prototypical enyne cycloisomerization...
Conference Paper
Full-text available
The past decade has witnessed a renewed interest for Secondary Phosphine Oxides (SPOs) as preligands of transition metals. [1] These air and moisture stable compounds exist in solution as a tautomeric equilibrium with Phosphinous Acids (PAs). This duality offers several coordination modes and roles to SPOs and PAs: preligand, monodentate ligand and...
Article
John Wiley & Sons, Hoboken, 2013. 830 S., geb., 152.00 €.—ISBN 978-1118148921
Article
John Wiley & Sons, Hoboken, 2013. 830 pp., hardcover, € 152.00.—ISBN 978-1118148921
Article
The enantioselective conjugate addition (ECA) of nucleophiles to electron-deficient alkenes represents one of the most powerful methods to form C. C or C-heteroelement bonds, which is widely used in total synthesis of complex chiral molecules. Dealing with the metal-catalyzed version, significant breakthroughs were accomplished in the past two deca...
Article
The goal of this Review is to provide a comprehensive overview of the major developments in enantioselective cobalt-catalyzed transformations. Reactions that form multiple bonds, rings and stereocenters are particularly important tools for the efficient assembly of complex molecular structures. The cyclopropanation of olefins using the transition-m...
Article
This chapter covers the recent developments in the [5+2] cycloaddition reaction, focusing on metal-catalyzed [5+2] cycloadditions, [5+2] cycloadditions of metal-containing 5C components, [5+2] cycloadditions of oxidopyrylium and pyridinium species, [5+2] photocycloadditions, and domino reactions including a [5+2] cycloaddition. Two reviews concentr...
Patent
Full-text available
Disclosed herein are compounds of the formula (I) or (II) in which: L is a neutral ligand; X, X′ are anionic ligands; R1 and R2 are, separately, a hydrogen, a C1-C6 alkyl, a C1-C6 perhalogenoalkyl, a aldehyde, a ketone, an ester, a nitrile, an aryl, a pyridinium alkyl, an optionally substituted C5 or C6 pyridinium alkyl, perhalogenoalkyl or cyclohe...
Conference Paper
Full-text available
Alkynes and hetero-substituted alkynes are useful synthons in organic synthesis as attested by the impressive number of reports dealing with their reactivity. Recent advances in the preparation of electron-deficient aza-substituted alkynes, ynamides, allowed the development of versatile transformations using theses substrates. [1] They represent an...
Article
The title reaction shows general applicability to various functionalized bicyclo[2.2.1]hept-2-enes, such as (I), (IV), (VII), (IX), and (XI) and ynamides.
Article
An efficient palladium‐catalyzed [2+1] cycloaddition between ynamides and norbornenes or norbornadienes is reported. Both phosphapalladacycles and palladium/secondary phosphine oxide catalytic systems were found to be competent for the transformation allowing the preparation of aminomethylenecyclopropanes. The reaction showed general applicability...
Article
Since the first definition of domino reactions by Tietze in 1993, an explosive number of these fascinating reactions has been developed, allowing the easily building of complex chiral molecular architectures from simple materials to be achieved in a single step. Even more interesting, the possibility to join two or more reactions in one asymmetric...
Article
Cycles everywhere: The selectivity in the transformations of 1,3-diones to carbocycles by palladium-catalyzed bisallylic alkylations is strongly dependent on the phosphine that is employed. Moreover, synthesized vinylcyclopentenes can be easily transformed into cycloheptadiene derivatives through a carbon-carbon allylic bond cleavage.
Article
A short synthetic route to phosphonate prodrugs by olefin cross-metathesis, which uses either (acyloxymethyl) or (hexadecyloxypropyl) allylphosphonate building blocks is described. A study of eight ruthenium catalysts including the Ru–indenylidene catalyst, which bears the N-heterocyclic carbene 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-...
Article
Platinum complex PPT catalyzes the unprecedented intermolecular sequence performed with norbornadiene and alkynes.
Article
Full-text available
Continuous flow homogeneous alkene metathesis using a supported ionic liquid phase (SILP) catalyst with CO2 as a transport vector allows the self-metathesis of methyl oleate with only a slight loss of activity for at least 10 h; cross-metathesis of dimethyl maleate with methyl oleate ceases after 3 h, but the catalyst remains active for methyl olea...
Article
The synthesis and characterization of two new ruthenium indenylidene complexes [RuCl(2)(SIPr)(Py)(Ind)] 6 and [RuCl(2)(SIPr)(3-BrPy)(Ind)] 7 featuring the sterically demanding N-heterocyclic carbene 1,3-bis(2,6-di isopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr) are reported. Remarkable activity was observed with these complexes in ring closin...
Article
A series of cationic gold(I) alpha-diimine complexes of the type [(NHC)Au(alpha-diimine)]X or [(PPh3)Au(alpha-diimine)]X, where NHC = IPr, alpha-diimine = BIAN-dipp, X = PF6 (1); X = BF4 (2); X = SbF6 (3); NHC = (IBu)-Bu-t, alpha-diimine = BIAN-dipp X = PF6 (4); X = BF4 (5); NHC = IMes, alpha-diimine = BIAN-dipp, X = PF6 (6); PPh3, alpha-diimine =...
Article
[6 + 2] Cycloadditions between cycloheptatrienes with allenes have been investigated. Cobalt salts were found to promote this transformation efficiently. Moreover, this reaction was found to be highly selective since only one regioisomer was obtained with an excellent E/Z-selectivity.
Article
Platinum complexes bearing phosphinous acids have efficiently promoted a tandem intermolecular sequence of [2+1]/[3+2] cycloaddition reactions. This process gave access to novel tricyclic systems and the cascade reactions were regio- and diastereoselective (see scheme; Cy=cyclohexyl). The [3+2] cycloaddition reaction was investigated further and tw...
Article
The steric and electronic properties of several sterically demanding tertiary phosphines (dicyclohexylphosphino)biphenyl (2a), 2-dicyclohexylphosphino-2′-methylbiphenyl (2b), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (2c), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (2d), 2-diphenylphosphino-2′-(N,N-dimethylamino)biphenyl (2e), 2-di...
Article
Full-text available
The steric and electronic influence of backbone substitution in IMes-based (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) N-heterocyclic carbenes (NHC) was probed by synthesizing the [RhCl(CO)₂(NHC)] series of complexes to quantify experimentally the Tolman electronic parameter (electronic) and the percent buried volume (%V(bur), steric)...
Article
The aim of the present study is to develop readily available and stable pre-catalysts that could be easily prepared on large scale from simple starting materials. Based on the hypothesis that substitution of classical PCy(3) with phosphanes of varying electron-donating properties could be a straightforward manner to improve catalytic activity, a me...
Article
Over the past decade, ruthenium-mediated metathesis transformations, including polymerization reactions, cross-metathesis, ring-closing metathesis, enyne metathesis, ring-rearrangement metathesis, and also tandem processes, represent one of the most studied families of organic reactions. This has translated into the development of a large number of...
Article
A series of second-generation ruthenium-based olefin metathesis catalysts bearing N-naphthyl-substituted N-heterocyclic carbene (NHC) ligands have been prepd. and fully characterized. By reaction with the appropriate NHC, these complexes are readily accessible in one synthesis step from the com. available first-generation precursors [RuCl2(:CHPh)(P...
Article
Electronic and steric ligand effects both play major roles in organometallic chemistry and consequently in metal-mediated catalysis. Quantifying such parameters is of interest to better understand not only the parameters governing catalyst performance but also reaction mechanisms. Nowadays, ligand molecular architectures are becoming significantly...
Article
Several ruthenium-indenylidene complexes bearing N-heterocyclic carbenes (NHCs) and phosphanes have been investigated for the ring rearrangement of cyclic compounds by alkene metathesis. These catalysts were found to promote efficiently such domino reactions, especially sterically hindered NHC-containing complexes. Moreover, indenylidene-type catal...
Chapter
Full-text available
Ruthenium-mediated olefin metathesis has emerged as an indispensable tool in organic synthesis for the formation carbon–carbon double bonds, attested by the large number of applications for natural product synthesis. Among the numerous catalysts developed to mediate olefin metathesis transformations, ruthenium–indenylidene complexes are robust and...
Article
Ruthenium-indenylidene complexes are robust and efficient precatalysts for olefin metathesis reactions. This report provides an overview of recent developments in the synthesis of ruthenium-indenylidene complexes and their applications in olefin metathesis transformations. The construction of the indenylidene moiety will be discussed as well as the...
Article
The synthesis and characterization of three novel trifluoromethylamido-containing “boomerang” precatalysts bearing various N-heterocyclic carbene (NHC) ligands are reported. Comparative kinetic and stability studies show the significant effect of the NHC on the catalyst reaction profile. An investigation of the reaction scope for diverse metathesis...
Article
A study on the enyne metathesis reaction leading to the formation cyclic compounds using ruthenium-indenylidene complexes is presented. Several 1,11-dien-6-ynes have been subjected to ruthenium metathesis cyclization by using ruthenium-indenylidene complexes bearing various phosphine and N-heterocyclic carbene (NHC) ligands. Interestingly, for some...
Article
The introduction of N-heterocyclic carbene ligands that incorporate correctly substituted naphthyl side chains leads to increased activity and stability in second generation ruthenium metathesis catalysts.
Article
The synthesis and characterization of a novel indenylidene-containing ruthenium catalyst bearing the N-heterocyclic carbene (NHC) ligand 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr) are reported. Comparative reactivity studies with other indenylidene complexes using various substrates show the importance of the sterically dem...
Article
Complexes of palladium bearing NHC ligands (NHC=N-heterocyclic carbene) were synthesized and fully characterized. The [Pd(NHC)(allyl)Cl] series was obtained by simple cleavage of [Pd(allyl)Cl]2 by using either the isolated free NHC or the in situ generated NHC. The NHC ligand sterics were varied by introduction of groups attached to the C4–C5 carbo...
Article
A comparative study examining the catalytic activity of a series of five indenylidene-containing ruthenium complexes in olefin cross-metathesis reactions is presented. Results reveal the greater efficiency of precatalyst 5, highlighting the key role of the N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) ligand for this transformation. The s...
Article
Starting from the corresponding dimer, new saturated NHC-containing N,N-dimethyl biphenylamine (DMBPA) palladacycle complexes have been synthesized and fully characterized. Catalytic activity of these well-defined, air- and moisture-stable palladium(II) complexes was evaluated in the Buchwald−Hartwig amination involving a range of unactivated aryl...
Article
Ruthenium-indenylidene complexes represent a class of robust and efficient pre-catalysts for olefin metathesis reactions. In this feature article, we provide an overview of the various complexes belonging to this family and summarise their use in various applications. The relation between the nature of ancillary ligands around the metal coordinatio...
Article
Three novel "boomerang" precatalysts bearing different aminocarbonyl functions are reported. Comparative kinetic studies show that this functional group allows for a control of the catalytic activity in metathesis transformations. The scope of the more active catalyst is investigated and shows a good tolerance to various substrates in ring-closing...
Chapter
In the last decade, coordination chemistry has witnessed the advent of a new class of ligands: the N-heterocyclic carbenes (NHCs). The “success story” associated with this ligand family can be explained by the unique stereoelectronic properties of the NHCs; these unique properties have led to their numerous applications in catalysis. This article p...
Article
Two new dicarbonyl N-heterocyclic carbene nickel(0) complexes of the type (NHC)2Ni(CO)2 (NHC = ICy, [N,N′-bis(cyclohexylimidazol)-2-ylidene (2), IMes [N,N′-bis(2,4,6-trimethylphenyl)imidazol)-2-ylidene] (3)) have been prepared by a substitution reaction of (NHC)Ni(CO)2 (NHC = ItBu [N,N′-bis(tert-butylimidazol)-2-ylidene], IAd [N,N′-bis(1-adamantyli...
Article
A new complex of ruthenium bearing the unsaturated N-heterocyclic carbene IMes (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and an ionic alkylidene moiety was synthesized and fully characterized. The X-ray structure of this catalyst and that of its SIMes (SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) analogue we...
Article
The ring opening metathesis polymerization (ROMP) of cycloocta- 1,5-diene (COD) is mediated by a series of six well-defined ruthenium-based indenylidene catalysts. The polymerization kinetics are monitored and compared with three generations of Grubbs' catalyst. Moderate control over the polymerizations was observed for both benzylidene and indenyl...
Article
The catalytic performances of three Phosphabicyclononane (Phoban)-containing ruthenium-based pre-catalysts have been evaluated for metathesis transformations. A wide screening of substrates in ring-closing metathesis reactions reveals the greater efficiency of pre-catalyst 4. Comparison of the catalytic activities of 4 with Grubbs' first-generation...
Article
Complexes of iridium bearing NHC (NHC = N-heterocyclic carbene) ligands were synthesized and fully characterized. The series [(NHC)Ir(cod)Cl] were obtained by simple cleavage of [Ir(cod)Cl]2. The [(NHC)Ir(cod)Cl] complexes were reacted with excess carbon monoxide, leading to [(NHC)Ir(CO)2Cl]. The infrared carbonyl stretching frequencies of these we...
Article
Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful transformation for the formation of new carbon-carbon double bonds. This area is now quite familiar to most chemists as numerous catalysts are available that enable a plethora of olefin metathesis reactions. Nevertheless, with the exception of uses in polymerizatio...
Article
Rutheniumkatalysierte Olefinmetathesen sind leistungsfähige Reaktionen zur Bildung von Kohlenstoff-Kohlenstoff-Doppelbindungen. Das Gebiet ist mittlerweile gut erforscht, zumal zahlreiche Katalysatoren erhältlich sind, die vielfältige Umwandlungen ermöglichen. Trotzdem gibt es, mit der Ausnahme von Polymerisationsprozessen, nur wenige industrielle...
Article
Full-text available
This report provides a critical overview of recent developments in the use of N-heterocyclic carbenes (NHCs) with transition metals. For these NHC ligand-containing complexes, an analysis is focused on their performance and scope in catalysis. There is also an increasing interest in the role of nucleophilic carbenes as organocatalysts; the latest a...