PUBLICATIONS
Boronic acids Synthesis
Scalable and reliable ! Non cryogenic !
Tetrahedron 2019, 164-171
Complete List of Publications
86. Synthesis of Tertiary Fluorides through an Acid-Mediated Deoxyfluorination of Tertiary Alcohols
Xavier Bertrand, Mathieu Pucheault, Laurent Chabaud,* Jean-Francois Paquin*, J. Org. Chem., 2023, asap
The combination of methanesulfonic acid and potassium bifluoride is reported for the deoxyfluorination of tertiary alcohols. Under metal-free conditions that use readily available, cheap, and easy-to-handle reagents, a range of tertiary alcohols could be converted into the corresponding fluorides in excellent yields (average yields of 85% for 23 examples). Mechanistic investigation showed that the reaction proceeds at 0 °C, in part, through an elimination/hydrofluorination pathway, but no residual alkenes are observed. The application of these conditions for the fluorination of ether and ester is also demonstrated.
85. Metal-Free Defluoroborylation of 3,3-Difluoropropenes
Rémy Ferlet, Mathieu Pucheault, Laurent Chabaud, Jean-François Paquin*, Eur. J. Org. Chem., 2023, e202300731
The defluorinative functionalization of allylic fluorides represents an attractive approach for the preparation of molecules containing a monofluoroalkene core. In that sense, introducing a “boryl nucleophile” is a powerful strategy to obtain polyvalent borylated intermediates as versatile synthetic precursors. To perform this reaction without the use of transition metals, the nucleophilic character of a diborane/fluoride system was exploited in a SN2′ type-substitution reaction of gem-difluoropropenes to install a pinacolborane group. The use of HMDS as a silylated additive is necessary to improve the reactivity. A direct oxidation of the intermediate boronates allowed the isolation of the corresponding β-fluoroallyl alcohols in low to good yields (9−81%). Other synthetic transformations of a (2-fluoroallyl)boronate are also illustrated..
84. Recent Advances in the Synthesis of Borinic Acid Derivatives
Marion Boyet; Laurent Chabaud;* Mathieu Pucheault*, Molecules, 2023, 28(6), 2660
Borinic acids [R2B(OH)] and their chelate derivatives are a subclass of organoborane compounds used in cross-coupling reactions, catalysis, medicinal chemistry, polymer or optoelectronics materials. In this paper, we review the recent advances in the synthesis of diarylborinic acids and their four-coordinated analogs. The main strategies to build up borinic acids rely either on the addition of organometallic reagents to boranes (B(OR)3, BX3, aminoborane, arylboronic esters) or the reaction of triarylboranes with a ligand (diol, amino alcohol, etc.). After general practical considerations of borinic acids, an overview of the main synthetic methods, their scope and limitations is provided. We also discuss some mechanistic aspects.
83. In situ generation of radical initiators using amine-borane complexes for carbohalogenation of alkenes
Virginie Liautard, Marine Delgado, Boris Colin, Laurent Chabaud, Guillaume Michaud and Mathieu Pucheault*, Chemical Communications, 2022, 58, 2124 – 2127
Atom transfer radical addition of alkyl halides to alkenes was developed using a low amount of a stable initiator, amine borane complexes. Thanks to a slow hydroboration step, the overall carbohalogenation process leads to good isolated yields
80.Using Catalysts To Make Catalysts: Titanium-Catalyzed Hydroamination To Access P,N-Ligands for Assembling Catalysts in One Pot
Han Hao, Thibault Bagnol, Mathieu Pucheault*, and Laurel L. Schafer* Org. Lett. 2021, 23, 1974-1979
Using a diamido-bis(amidate) titanium precatalyst, the hydroamination of alkynylphosphines afforded phosphinoenamine products. After reduction, 2-aminophosphines are prepared in excellent yield and on gram scale. A broad variety of alkynylphosphines and primary amines with different electronic and steric features are tolerated in this sequential transformation, enabling the rapid assembly of a collection of ligands. Additionally, intermediate phosphinoenamines can be used directly as proligands for coordination to transition metals using protonolysis or salt metathesis reactions. These transformations result in easy-to-use one pot protocols to prepare metal P,N-complexes for catalysis or small molecule activation.
79. Amine–borane complex-initiated SF5Cl radical addition on alkenes and alkynes
Audrey Gilbert, Pauline Langowski, Marine Delgado, Laurent Chabaud, Mathieu Pucheault, Jean-François Paquin, Beilstein Journal of Organic Chemistry 2020, 16, 3069-3077
The SF5Cl radical addition on unsaturated compounds was performed using an air-stable amine–borane complex as the radical initiator. This method showed to be complementary to the classic Et3B-mediated SF5Cl addition on alkenes and alkynes. A total of seven alkene and three alkyne derivatives were tested in the reaction, with yields ranging from 3% to 85%.
78. Synthesis and Characterization of Store-Operated Calcium Entry Inhibitors Active in the Submicromolar Range
Camille le Guilcher, Tomas Luyten, Jan B. Parys, Mathieu Pucheault, Olivier Dellis Int. J. Mol. Sci. 2020, 21(24), 9777
The store-operated calcium entry, better known as SOCE, forms the main Ca2+ influx pathway in non-excitable cells, especially in leukocytes, where it is required for cell activation and the immune response. During the past decades, several inhibitors were developed, but they lack specificity or efficacy. From the non-specific SOCE inhibitor 2-aminoethyl diphenylborinate (2-APB), we synthetized 16 new analogues by replacing/modifying the phenyl groups. Among them, our compound P11 showed the best inhibitory capacity with a Ki ≈ 75 nM. Furthermore, below 1 µM, P11 was devoid of any inhibitory activity on the two other main cellular targets of 2-APB, the IP3 receptors, and the SERCA pumps. Interestingly, Jurkat T cells secrete interleukin-2 under phytohemagglutinin stimulation but undergo cell death and stop IL-2 synthesis when stimulated in the presence of increasing P11 concentrations. Thus, P11 could represent the first member of a new and potent family of immunosuppressors
Marine Delgado, Guillaume Michaud, Boris Colin, Frédéric Simon, Stéphane Fouquay, Mathieu Pucheault 16/04/2020 FR2003811
Marine Delgado, Guillaume Michaud, Boris Colin, Frédéric Simon, Stéphane Fouquay, Mathieu Pucheault 16/04/2020 FR2003810
75. Non-biaryl Atropisomerism at C–B Bond in Sterically Hindered Aminoarylboranes
Mélodie Birepinte, Frédéric Robert, Sandra Pinet, Laurent Chabaud, Mathieu Pucheault, Org. Biomol. Chem. 2020, 3007-3011
Sterically hindered aminoarylboranes featuring atropisomerism about the C–B bond were prepared by addition of organomagnesium species onto readily accessible dialkylamine-borane complexes. Some of these aminoarylboranes, isosteres of vinyl styrene derivatives, were resolved by HPLC on chiral stationary phase. They are the first examples of non-biaryl type system which display slow rotation about a C–B bond
Mélodie Birepinte, Virginie Liautard, Laurent Chabaud, Mathieu Pucheault, Org. Lett. 2020, 22, 7, 2838–2843
A simple procedure has been optimized for the preparation of alkenylaminoborane from alkynes using diisopropylaminoborane and HZrCp2Cl. Coupled with a magnesium-catalyzed dehydrogenation, it allowed for the use of air- and moisture-stable diisopropylamine. This synthesis has been extended to a one-pot sequence leading directly to bromoalkenes with controlled stereochemistry. As such, it provides an easy, scalable, cheap process to access alkenylboronates and both (E)- and (Z)-bromoalkenes from commercially available alkynes.
Mélodie Birepinte, Virginie Liautard, Laurent Chabaud, Mathieu Pucheault, Chem Eur J 2020, 3236-3240.
Owing to the unusual reactivity of sterically hindered amine–borane complexes, a catalytic system based on magnesium salts was designed to perform a tandem dehydrogenation–dehydrocoupling between terminal alkynes and boranes. The reaction is providing pure alkynylboranes within few minutes at room temperature, with only two molecules of hydrogen as a byproduct.
Virginie Liautard, Mathieu Pucheault, FR Demand FR 19 11003, 04/10/2019
Mélodie Birepinte, Mathieu Pucheault, FR Demand FR 19 11003, 04/10/2019
Guillaume Michaud, Boris Colin, Frédéric Simon, Stéphane Fouquay, Virginie Liautard, Mathieu Pucheault FR Demand FR 19 08161, 18/07/2019
Guillaume Michaud, Frédéric Simon, Stéphane Fouquay, Virginie Liautard, Mathieu Pucheault, Boris Colin FR Demand FR 19 08159, 18/07/2019
Olivier Dellis, Camille Chalvin, Mathieu Pucheault, FR Demand FR 19 07184, 28/06/2019
Ludovic D. Marciasini, Jimmy Richard, Bastien Cacciuttolo, Guillaume Sartori, Melodie Birepinte, Laurent Chabaud, Sandra Pinet, Mathieu Pucheault
Tetrahedron 2019, 164-171
Owing to the unusual reactivity of dialkylamine-borane complexes, a methodology was developed to simply access boronic acids. The intrinsic instability of magnesium aminoborohydride was tweaked into a tandem dehydrogenation borylation sequence. Proceeding via an autocatalytic cycle, amineborane dehydrogenation was induced by a variety of Grignard reagents. Overall, addition of the organomagnesium species onto specially designed dialkylamine-borane complexes led to a variety of boronic acids in high yields. In addition, the reaction can be performed under Barbier conditions, on a large scale
66. Mg-Catalyzed OPPenauer Oxidation—Application to the Flow Synthesis of a Natural Pheromone
Virginie Liautard, Mélodie Birepinte, Camille Bettoli, Mathieu Pucheault
Catalysts 2018, 529-536
The so-called OPPenauer oxidation is well known for its ability to oxidize valuable alcohols into their corresponding aldehydes or ketones. In particular, it has proven to be extremely successful in the oxidation of sterols. On the other hand, its application—in the original formulation—to the obtainment of ketones outside the field of steroids met a more limited success because of less favorable thermodynamics and side reactions. To circumvent these issues, the first example of magnesium-catalyzed OPPenauer oxidation is described. The oxidation of primary and secondary alcohol was performed using pivaldehyde or bromaldehyde as the oxidant and cheap magnesium tert-butoxide as catalyst. Decent to excellent yields were obtained using reasonable catalytic charge. The synthesis of a pheromone stemming from the Rhynchophorus ferrugineus was obtained by tandem addition-oxidation of 2-methylpentanal and the process was successfully applied to continuous flow on a multigram scale.
65. Dehydrogenative Silylation of Alcohols Under Pd-nanoparticule Catalysis
Chem Eur. J. 2019, 728-732
Pd-nanoparticle catalyzed dehydrogenative coupling between various hydrosilanes and alcohols was shown to provide silyl ethers in good and reproducible yields. The synthetic methodology is effective for a wide range of simple and bulky silanes and secondary alcohols, while keeping various other functional groups intact. The procedure also exhibits high selectivity for the silylation of primary versus secondary alcohols in 1,2-diols, and allows the successive silylation of alkynols and hydrogenation of the triple bond to afford Z-alkenols in good yields.
P. Giorgi, V. Liautard, M. Pucheault, S. Antoniotti Eur J. Org. Chem, 2018, 1307-1311
Using a combination of Au nanoparticle‐catalyzed oxidation under an O2 atmosphere and a Ti‐doped montmorillonite (Ti‐MMT)‐catalyzed tandem arylation/double cyclization, we developed an original and highly selective method for the synthesis of ortho‐tetrahydrocannabinol derivatives from simple substrates. The reaction sequence could be performed in two steps in batch mode or in a single operation in continuous‐flow reactors. The abnormal regioselectivity was proposed to be the result of the non‐innocent role of the MMT support, TiIV cation coordination, and a Lewis acid‐assisted Brønsted acid (LBA) mechanism
63. Nouveau procédé de stockage de l’hydrogène
Mathieu Pucheault FR Demand 1758543, 2017
62. Instant One-Pot Preparation of Functional Layered Double Hydroxides (LDH) via a Continuous Hydrothermal Approach
O. Pascu, S. Marre, B. Cacciuttolo, G. Ali, L. Hecquet, M. Pucheault, V. Prevot, C. Aymonier
Instant one‐pot synthesis of functional layered double hydroxides (LDHs) is demonstrated for the first time using a continuous hydrothermal multi‐step process. The as‐prepared pristine material displays high crystallinity and very small LDH nanoparticle size, lateral dimensions below 100 nm and a thickness below 20 nm, all being achieved in only 5 s. This approach was extended to the preparation of i) pristine LDH with different compositions by varying the cation (Mg, Ni, or Zn) and the anion (CO3, NO3) and ii) functional LDH by varying the functionalization agent, for example long organic molecules (hybrid LDH), enzymes (bio‐hybrid LDH) or inorganic metal/oxide nanocrystals (inorganic‐LDH). Beyond the design of functional LDH, this paper presents proof of concept for a continuous, one‐pot and multistep high temperature/high pressure (HT/HP) process for the assembly of nanoscaled materials.
61. Nouveau procédé d’oxydation des alcools primaires et secondaires
Mathieu Pucheault, Virginie Liautard
FR Demand 1755390, 2017
60. Radical Metal-Free Borylation of Aryl Iodides
Sandra Pinet, Virginie Liautard, Mégane Debiais, Mathieu Pucheault
Synthesis , 2017, 49 4759-4768
special topic “Modern Strategies for Borylation in Synthesis”
A simple metal-free borylation of aryl iodides mediated by a fluoride sp2–sp3diboron adduct is described. The reaction conditions are compatible with various functional groups. Electronic effects of substituents do not affect the borylation while steric hindrance does. The reaction proceeds via a radical mechanism in which pyridine serves to stabilize the boryl radicals, generated in situ.
59. Nouvelle composition d’isomères du 7,9-dodécadiényl-1-acétate et son procédé de fabrication
Mathieu Pucheault, Virginie Liautard, Loic Guillonneau, Olivier Guerret
FR Demand FR1751979, 2017
58. Borinic Acids via Direct Arylation of Amine–Borane Complexes : An Air- and Water-Stable Boron Source
Richard, Jimmy ; Birepinte, Mélodie ; Charbonnier, Jean Baptiste ; Liautard, Virginie ; Pinet, Sandra ; Pucheault, Mathieu
Synthesis , 2017, 49 736-744
A synthesis of borinic acids and borinates was optimized using amine–borane complexes as a water and air insensitive borylating agent. The reaction operates under convenient conditions using a non-cryogenic temperature and with no flash chromatography, and it gives no boron impurities. The reaction proceeds through a tandem dehydrogenation–double addition mechanism.
57. Pd@[nBu4][Br] as a Simple Catalytic System for N-Alkylation Reactions with Alcohols
Bastien Cacciuttolo, Oana Pascu, Cyril Aymonier, Mathieu Pucheault
Molecules, 2016, 1042-1055
special Issue Cascade Catalysis
Palladium nanoparticles, simply and briefly generated in commercial and cheap onium
salts using supercritical carbon dioxide, have been found to be an effective catalytic system for
additive free N-alkylation reaction using alcohols via cascade oxidation/condensation/reduction s
56. Highly efficient Hosomi-Sakurai reaction of aromatic aldehydes catalyzed by Montmorillonite doped with simple bismuth(III) salts. Batch vs continuous flow studies
Nelli Elizarov, Mathieu Pucheault and Sylvain Antoniotti
Chemistry Select, 2016, 3219-3222
Montmorillonite doped with simple bismuth(III) salts was found to be an efficient catalyst for the Hosomi‐Sakurai allylation of aldehydes. The reaction was performed on different substituted aromatic aldehydes with allyl and methallyl trimethylsilanes. In contrast with most existing methods typically leading to alcohols with the loss of the silyl group, or to mixtures of free and silylated alcohols, our catalytic system delivered selectively in mild conditions and 71–96 % yields the corresponding protected alcohols which could be further used in a larger synthetic scheme. The reaction was easily transferred in continuous flow with maintained efficiency and superior scalability.
55. Simple salts of abondant metals (Fe, Bi, and Ti) supported on Montmorillonite as efficient and recyclable catalysts for regioselective intramolecular and intermolecular hydroalkoxylation reactions of double bonds and tandem processes
Irene Notar Francesco, Bastien Cacciuttolo, Oana Pascu, Cyril Aymonier, Mathieu Pucheault and Sylvain Antoniotti
RSC Adv., 2016, 6, 19807–19818
The transfer of catalytic hydroalkoxylation reactions of olefins from homogeneous to heterogeneous conditions has been studied using two types of solid catalysts, namely montmorillonite (MMT) doped with metal cations and metal nanoparticles supported on oxides. In the case of intramolecular reactions, 38–99% yields of cyclic ethers have been obtained using Fe-MMT and Bi-MMT both in CH3NO2 and dimethyl carbonate (DMC) compared with other supported metal salts or metal nanoparticles. In the case of more challenging intermolecular reactions, conversions up to 72% and yields up to 54% were obtained with metal-doped MMT as well, such as Fe-, Bi-, and Ti-MMT. In this paper, we detail the substrate scope and limitations for both classes of reactions and tandem processes, their transposition in flow and some mechanistic insights concerning the active species, in processes identified as truly heterogeneously catalysed. As a general trend, it was observed that trisubstituted double bonds allowed the best results both in intra- and intermolecular reactions. The transfer of homogeneous catalysts onto heterogeneous ones in the case of Fe-MMT and Bi-MMT was successful and even allowed enhanced catalytic activities in the case of Bi-MMT.
54. Synthesis of borinic acids and borinate adducts using diisopropylaminoborane
L. Marciasini, B. Cacciuttolo, M. Vaultier, M. Pucheault
Org Lett., 2015, 3532-3535
n situ formation of aryl Grignard under Barbier condition and diisopropylaminoborane as boron source allows a complete control of the addition onto the boron electrophile. Analytically pure borinic acid derivatives were produced at the gram scale without column chromatography and isolated as borinates adducts, with ethanolamine or 8-hydroxyquinoline, after workup.
53. Procédé de préparation, d’un acide boronique, d’un acide borinique ou de leur dérivés
M. Pucheault, M. Vaultier, B. Cacciuttolo, L. Marciasini
16/06/2015, FR15/555515
52. Advanced Nanostructured Catalysts for Hydroboration
Virginie Liautard, Oana Pascu, Cyril Aymonier, Mathieu Pucheault
Catalysis Today, 2015, 255, 60-65 Special Issue “Green Catalysis”
Metal nanocrystals have been prepared in onium salts using supercritical carbon dioxide assisted synthesis. During the process, metal salts precursors are reduced by H2 in an organic solvent free media, the onium salts allowing both the stabilization of the nanostructured material and the preparation of an air and moisture stable powder made of embedded metal nanocrystals. Those catalysts proved to be highly effective in the hydroboration of alkyne process.
51. Simple metal salts supported on montmorillonite as recyclable catalysts for intramolecular hydroalkoxylation of double bonds in conventional and VOC-exempt solvents
I. Notar Francesco, B. Cacciuttolo, M. Pucheault and S. Antoniotti
Green Chem., 2015, 17, 837-841.
We describe herein an efficient and particularly sustainable catalytic system for the intramolecular hydroalkoxylation of double bonds. A heterogeneous catalyst based on the impregnation of benign metals such as iron and bismuth on montmorillonite was used for a highly atom-economic transformation in DMC, a non-VOC solvent. The transformation allowed the formation of a large range of cyclic ethers from the corresponding unsaturated alcohols and the catalyst could be recycled several times.
50. Amine–Borane Complexes : Air- and Moisture-Stable Partners for Palladium-Catalyzed Borylation of Aryl Bromides and Chlorides
H. D. S. Guerrand, M. Vaultier, S. Pinet and M. Pucheault
Adv. Synth. Catal., 2015, 6, 1167-1174
A method for using amine–borane complexes directly in palladium catalyzed borylation has been developed. The reaction proceeds through the sequential formation of a boronium species followed by deprotonation leading to the aminoborane. This reagent is then directly used in the borylation process leading, after work‐up, to various boronic acid derivatives. The reaction was applied to (hetero)aryl triflates, iodides, bromides and chlorides.
49. ScCO2 assisted preparation of supported metal NPs. Application to catalyst design
O. Pascu, B. Cacciuttolo, S. Marre, M. Pucheault, and C. Aymonier
J. Supercritical Fluids, 2015 105, 84-91
Designing and developing materials with specific properties are nowadays important tasks. These could be achieved by choosing the adequate conditions, from a myriad of possibilities, being aware that slight changes in the preparation method could have major impact on the final material. With the work presented here, we are showing that kinetically controlled surface nano-structuring (NPs formation and deposition over solid supports) in scCO2 is a versatile way for preparing active materials. Size, composition, morphology and organization/architecture of supported metal NPs can be controlled by playing with the type of metal, metal precursor, reaction media composition (stronger or weaker reducing media) and different supports employed. Moreover, direct correlation between physical (size, morphology, organization) and chemical properties (composition, surface chemistry) are demonstrated with the systems catalytic behaviour, yield and selectivity, exemplified with N-alkylation reaction of amines with alcohols.
48. Catalysed stereodivergent hydrosilylation with Onium Salts stabilised M(0) Nanocatalysts prepared in scCO2
O. Pascu, V. Liautard, M. Vaultier, M. Pucheault, and C. Aymonier
RSC Advances, 2014, 4 (104), 59953 - 59960
M(0) nanocatalysts stabilised in Onium Salt were synthesised using an original preparation and their effectiveness in catalysing the challenging selective sterodivergent alkyne hydrosilylation reaction was studied. Four metal based nanocrystals, namely Pt, Ir, Rh and Ru stabilised by three Onium Salts (quaternary ammonium salts with different anions and cations), were successfully prepared by supercritical CO2 assisted synthesis. The Onium Salts with three different structures were chosen considering their effect on nanocrystals morphology and surface properties but without interference in the selectivity towards hydrosilylation reaction. It was found that the stereochemical outcome can be adjusted either by varying the metal but preserving the same Onium Salt stabilizer, or varying the metal NCs surface properties by changing the stabilizer structure.
47. Glycosylation with N-acetyl glycosamine donors using catalytic iron(III) triflate : from microwave batch chemistry to a scalable continuous-flow process
Amandine Xolin, Arnaud Stévenin, Mathieu Pucheault, Stéphanie Norsikian, François-Didier Boyer, Jean-Marie Beau
Org. Chem. Front., 2014, 6156-6161
Efficient and highly selective glycosylation reactions of peracetylated β-D-N-acetyl gluco- and galactosamine are described using catalytic iron(III) triflate under microwave conditions or in a continuous flow process. Simple β-glycosides and β-(1 → 6), β-(1 → 2) and β-(1 → 3) linked disaccharides bearing various protecting groups were obtained in high yields. Insights into the glycosylation mechanism are discussed.
46. PROCEDE DE PREPARATION D’ACIDES BORINIQUES
Mathieu Pucheault, Michel Vaultier, Ludovic D. Marciasini, Bastien Cacciuttolo
French Patent Demand, n° FR 16/54424 16/05/2014.
45. PROCEDE DE PREPARATION DE COMPOSE AROMATIQUE MANDELIQUE ET DE COMPOSE ALDEHYDE AROMATIQUE
L. Garel, K. Olivon, O. Back, F. Sarrazin, M. Pucheault
French Patent Demand, n° FR , FR 13 61169 15/11/2013.
44. Sequential dehydrogenation–arylation of diisopropylamine–borane complex catalyzed by palladium nanoparticles
Hélène D.S. Guerrand, Ludovic D. Marciasini, Thomas Gendrineau, Oana Pascu, Samuel Marre, Sandra Pinet, Michel Vaultier, Cyril Aymonier, and Mathieu Pucheault
Tetrahedron, 2014, 6156-6161
Palladium nanoparticles have been prepared using different techniques, CO2-assisted microfluidics coflow or thermolysis using ionic liquids. Both techniques displayed interesting activities in dehydrogenation of diisopropylamine–borane complex, and allowed performing a dehydrogenation–arylation sequence with the creation of a carbon–boron bond.
43. Borylation of Unactivated Aryl Chlorides under Mild Conditions by Using Diisopropylaminoborane as a Borylating Reagent
Hélène D.S. Guerrand, Ludovic D. Marciasini, Mélissa Jousseaume, Michel Vaultier, Mathieu Pucheault
Chem. Eur. J., 2014, 5573–5579
The synthesis of arylboronic ester derivatives from aryl chlorides by using aryl(amino)boranes is described. Palladium‐catalyzed coupling between aryl chlorides and diisopropylaminoborane leads to the formation of a CB bond under mild conditions. A wide range of functional groups are tolerated, making this method particularly useful for the borylation of functionalized aromatics.
42. Comparison of homogeneous and heterogeneous Ga(III)-catalysis in the cycloisomerisation of 1,6-enynes
Khadija Ben Hadj Hassen, Kevin Gaubert, Michel Vaultier, Mathieu Pucheault and Sylvain Antoniotti
Green Chemistry Letters and Reviews, 2014, 243-249.
We describe a study of the gallium(III)-catalyzed 1,6-enynes cycloisomerization reaction in both homogeneous and heterogeneous conditions. With GaBr3 in homogeneous conditions, some particularities were observed in terms of selectivity compared to reported GaCl3-catalyzed reactions. The transfer of the reaction in heterogeneous conditions was realized by supporting Ga(III) salts onto montmorillonite. Both systems were compared based on reaction times, conversion, and selectivity and showed complementary activities.
41. Book Chapter : Ionic Liquids
Hélène D.S. Guerrand, Michel Vaultier, Mathieu Pucheault
Green Process Engineering : From concepts to the industrial applications, 2014
40. A new route towards fluorescent organic nanoparticles with red-shifted emission and increased colloidal stability
Kassem Amro, Jonathan Daniel, Guillaume Clermont, Talia Bsaibess, Mathieu Pucheault, Emilie Genin, Michel Vaultier, Mireille Blanchard-Desce
Tetrahedron, 2014, 70 (10), 1903-1909.
Suzuki–Miyaura cross-coupling reaction with a new boron reagent has been used to conveniently and efficiently synthetize a dipolar chromophore having an elongated π-conjugated system (i.e., bithiophene based), which displays a red-shifted emission while maintaining fluorescence. Bright orange emitting FONs made from this ‘naked’ dipole have been easily prepared and studied. Very interestingly, these FONs with red-shifted emission combine markedly enhanced colloidal and structural stability in water with giant one- and two-photon brightness. As such, they hold promises as fluorescent probes for bioimaging
39. Borylation using group IV metallocene under mild conditions
Ludovic D. Marciasini, Michel Vaultier, Mathieu Pucheault
Tetrahedron Lett., 2014, 1702–1705
A borylation reaction of aromatic diazonium salts has been optimized using titanocene and zirconocene derivatives as catalysts. The reaction employs diisopropylaminoborane as a borylating agent and proceeds smoothly at room temperature to provide arylboronates after methanolysis and transesterification with pinacol. The reaction mechanism has been found to proceed via a radical pathway.
38. A Green Approach for Producing Solvent-free Anisyl Acetate by Enzyme-catalyzed Direct Esterification in Sponge-like Ionic Liquids Under Conventional and Microwave Heating
Pedro Lozano, Juana M. Bernal, Almudena Lajarin, Daniel Romera, Eduardo Garcia-Verdugo, Gregorio Sanchez-Gomez, Mathieu Pucheault, Michel Vaultier, M. Isabel Burguete and Santiago V. Luis
Curr. Green Chem., 2014, 145-154
The biocatalytic synthesis of anisyl acetate fragrance was carried out by direct esterification of acetic acid with anisyl alcohol in sponge-like ionic liquids (SLILs), e.g. N,N,N,N-hexadecyltrimethylammonium bis(trifluoromethylsulfonyl) imide ([C16tma][NTf2], N,N,N,N-octadecyltrimethylammonium bis(trifluoromethylsulfonyl)imide ([C18tma] [NTf2]), etc. as reaction/separation media under conventional and microwave (MW) heating. These SLILs are temperatureswitchable ionic liquid/solid phases that behave as sponges. As liquid phases, they are excellent monophasic reaction media for the lipase-catalyzed synthesis of anisyl acetate, the product yield being improved up to 100% for 2 hour reaction under the appropriate reaction conditions (i.e. SLIL concentration, alcohol: acid molar ratio, enzyme amount, dehydrating molecular sieves, temperature and MW heating). As a function of the phase behaviour of different SLIL/anisyl acetate mixtures, a new clean separation protocol based on the centrifugation of the solid IL/flavour ester through nylon membranes was proposed, which provided a nearly full separation of the solid SLIL and the easy recovery of the reaction mixture. The enzymatic synthesis of anisyl acetate in [C16tma] [NTf2] under MW assistance, followed by the separation step of the solid SLIL, provided a nearly solvent-free fragrance product with up to 0.89 g/mL concentration. The catalytic activity of the enzyme / SLIL system remained unchanged for ten consecutive operational cycles. This work reports a straightforward and sustainable approach for producing anisyl acetate as a natural flavour and demonstrates to be suitable for scaling-up, providing a high potential for practical application.
37. METHOD FOR PREPARING AMINOARYLBORANE COMPOUNDS OR DERIVATIVES THEREOF
Ludovic D. Marciasini, Hélène Guerrand, Michel Vaultier, Mathieu Pucheault
European Patent Demand, n° EP 13306667.0 04/12/2013
36. Iron catalysis and water, a synergy for refunctionalisation of boron
John L. Wood, Ludovic D. Marciasini, Michel Vaultier, Mathieu Pucheault
Synlett, 2014, 25, 551-555.
A new catalytic system has been optimized to promote the conversion of boron species into others. FeCl3 associated with imidazole and water favors boron refunctionalization under mild conditions.
35. Continuous coflow synthesis of hybrid Palladium nanocrystals as catalysts for borylation reaction
Oana Pascu, Ludovic D. Marciasini, Samuel Marre, Michel Vaultier, Mathieu Pucheault, Cyril Aymonier
NanoScale, 2013, 5, 12425-12431
The combination of highly active Pd nanocrystal (NC) types with tailored surface properties (various ligands) – e.g. organic–inorganic hybrid NCs – as catalysts opens avenues towards new synthetic pathways, implying a faster practical alternative for adjusting and screening the reaction conditions. Pd@dppf and Pd@PCy3 NCs have been successfully prepared via a continuous supercritical fluid assisted coflow route with promising results as catalysts in borylation reaction. It has been found that the ligands not only influence the catalytic properties of the systems, but also contribute to Pd metal core characteristics (size, shape and time stability).
34. Iron-Catalysed Borylation of Arenediazonium Salts to Give Access to Arylboron Derivatives via aryl(amino)boranes at Room Temperature
Ludovic D. Marciasini, Nicolas Richy, Michel Vaultier, and Mathieu Pucheault
Adv. Synth. Catal., 2013, 355, 1083–1088
Complementary to previously described Miyaura borylation methods, a new access to boron derivatives via aryl(amino)boranes is described. Direct coupling between aryldiazonium salts and diisopropylaminoborane is catalysed by 0.1% ferrocene leading to the formation of a carbon‐boron bond. The obtained aryl(amino)boranes could eventually then be transformed into boronic acids, boronates or borates.
33. NOUVEAU PROCEDE DE SYNTHESE DU 3,4-DIMETHOXYBICYCLO[4.2.0]OCTA-1,3,5-TRIENE-7-CARBONITRILE, ET APPLICATION A LA SYNTHESE DE L’IVABRADINE ET DE SES SELS D’ADDITION A UN ACIDE PHARMACEUTIQUEMENT ACCEPTABLE
L. Vaysse-Ludot, A. Le Flohic, M. Vaultier, M. Pucheault, T. Kaminski
US Patent, FR3005658, US8859763, WO2014184501 17/05/2013
32. Supercritical Synthesis of Biodiesel
Juana M. Bernal, Pedro Lozano,* , Eduardo García-Verdugo, M. Isabel Burguete, Gregorio Sánchez-Gómez, Gregorio López-López, Mathieu Pucheault, Michel Vaultier and Santiago V. Luis
Molecules, 2012, 17, 8696-8719
The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats) has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercritical fluid (SCF) technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercritical fluids (SCFs) for biodiesel synthesis.
31. NEW PROCESS FOR PREPARING ARYLBORANES BY ARYLATION OF ORGANOBORON COMPOUNDS
Mathieu Pucheault, Ludovic Marciasini , Michel Vaultier
European Patent Demand, n° 12 305 854.7 WO2014009169 13/07/2012
30. Microfluidic Synthesis of Palladium Nanocrystals Assisted by Supercritical CO2 : Tailored Surface Properties for Applications in Boron Chemistry
Thomas Gendrineau, Samuel Marre, Michel Vaultier, Mathieu Pucheault,*, Cyril Aymonier,* Angew. Chem. Int. Ed., 2012, 51, 8653–8656.
On the surface: A library of organic–inorganic hybrid palladium nanocrystals was synthesized using continuous supercritical microfluidic technology. The nanocatalysts show moderate to excellent activities towards CAr-B and CAr-CAr bond‐forming reactions, thus illustrating the relationship between surface properties and modulated catalytic activity.
29. Aminoborylation/Suzuki–Miyaura tandem cross coupling of aryl iodides as efficient and selective synthesis of unsymmetrical biaryls
Ludovic Marciasini , Nicolas Richy , Michel Vaultier and Mathieu Pucheault
Chem. Commun., 2012, 48, 1553-1555
Sequential borylation of a first aryl iodide using a dialkylaminoborane followed by a Suzuki–Miyaura cross coupling of second aryl iodide ended up with an efficient, selective and practical synthesis of unsymmetrical biaryls. This tandem coupling shows a wide range of applicability.
28. Book Chapter : Product subclass 28 : Vinyl boranes
Mathieu Pucheault and Michel Vaultier
Science of Synthesis 2012, 297-341
27. Achieving chemo-, regio- and stereoselectivity in palladium-catalyzed reaction of gamma-borylated allylic acetates
Krishna Kishore Kukkadapu, Aziz Ouach, Pedro Lozano, Michel Vaultier, Mathieu Pucheault
Organic Letters 2011, 13, 15, 4132-4135.
Three-carbon highly functionalized γ-borylated allylic acetates underwent a regio- and stereocontrolled Tsuji-Trost reaction in the presence of
palladium complexes. An ipso substitution of the acetate with complete stereoretention of the chiral center was achieved, leading to vinylic
boronates with enantiomeric excesses above 99%.
26. Stabilizing immobilized cellulase by ionic liquids for saccharification of cellulose solutions in 1-butyl-3-methylimidazolium chloride
Pedro Lozano,, Berenice Bernal, Juana M. Bernal, Mathieu Pucheault and Michel Vaultier
Green Chemistry 2011, 13, 1406-1410
A new approach to improve the cellulase stability against 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), based on coating of immobilized enzyme particles with hydrophobic ILs, is proposed. The stability of commercial cellulase (Celluclast®), immobilized onto a polymeric support (Amberlite XAD4), was first studied in ten different ionic liquids (ILs) at 50 and 80 °C. Hydrophobic ILs clearly enhanced the enzyme thermal stability. Butyltrimethyl-ammonium bis(trifluoromethylsulfonyl)imide ([N1114][NTf2]) enhances half-life time of the immobilized enzyme at 50 °C up to 4 times, while [Bmim][Cl] behaved as a powerful enzyme deactivating agent. Thus, the stability of cellulase in hydrophobic IL/[Bmim][Cl] mixtures was greatly improved with respect to [Bmim][Cl] alone. A stabilized cellulase derivative obtained by coating immobilized enzyme particles with [N1114][NTf2], has been then successfully used for the saccharification of dissolved cellulose in [Bmim][Cl] (i.e. up to 50% hydrolysis in 24 h) at 50 °C and 1.5 w/v water content.
25. (Bio)catalytic continuous flow processes in scCO2 and/or ILs: Towards Sustainable (Bio)catalytic Synthetic Platforms.
Pedro Lozano, Eduardo Garcia-Verdugo, Santiago V. Luis, Mathieu Pucheault, Michel Vaultier
Current Organic Synthesis 2011, 14, 810-823.
This review highlights the tool box for the development of continuous green/sustainable processes aimed at the synthesis of
fine chemicals. By combining either chemical and/or biological catalysts with biphasic systems based on neoteric solvents, e.g. ionic liquids
(ILs) and supercritical carbon dioxide (scCO2), interesting alternatives to organic solvents for designing continuous clean
(bio)transformations methods are growing that directly provide pure products. The classical advantages of scCO2 –its ability to extract,
dissolve and transport chemicals– are complemented by the high catalytic efficiency of enzymes in ILs. Enzyme behavior in scCO2 and
ILs, as well as the phase behavior of ILs/scCO2, are key parameters for carrying out integral green bioprocesses in continuous operation.
The preparation, main characteristics and advantages of monolithic microreactors and miniflow reactors for the synthesis of fine chemicals
by continuous flow (bio)catalytic processes are underlined. Examples where the use of continuous flow techniques for multi-step
synthesis enables multiple reaction steps to be combined into a single continuous operation are provided.
24. Onium Salt Supported Peptide Synthesis
Céline Roche, Mathieu Pucheault, Michel Vaultier, Alain Commercon
Tetrahedron 2010, 8325-8334
Task specific ionic liquids and onium salts have been used as soluble supports for peptide synthesis. These new supports combine easy monitoring, high loading capacities, large scale preparation, and homogeneous kinetics characteristics while keeping advantages of solid-phase synthesis including easy purification and workup. Careful structural design of these supports allowed for fine tuning of physical properties leading to better yields, kinetics, and purities.
23. Exceptional Efficiency of Palladium Nanoparticles Catalyzed Heck Cross-coupling in Binary Task Specific Ionic Liquids
Fatima Hassine, Mathieu Pucheault, Michel Vaultier
Comptes Rendus Chimie 2011, 14, 7-8, 671-679
The utilization of the task specific onium salt supported substrates in ionic liquids as solvents (i.e., binary task specific ionic liquids) for palladium nanoparticle catalyzed Heck cross-coupling reactions is presented. Adequate substrates have been prepared and used leading to expected products in very high yields. Exceptionally high turnover (TON = 940,000, TOF = 208,000) can be achieved taking advantages of this combination. Additional advantages of this technology reside in the monitoring of the reaction and purification of products after degrafting which are simplified to the extreme.
22. Mild, base-free copper-catalyzed N-arylations of heterocycles using potassium aryltrifluoroborates in water under air
Nicolas Joubert, Emmanuel Baslé, Michel Vaultier, Mathieu Pucheault
Tetrahedron Letters, 2010, 2994-2997.
An economic, mild and efficient copper-catalyzed methodology for the N-arylation of heterocycles was optimized using potassium aryltrifluoroborates in water.
21. Review : Protein Chemical Modification on Endogenous Amino Acids
Emmanuel Baslé, Nicolas Joubert, Mathieu Pucheault
Chemistry and Biology, 2010, 213-227.
Chemical modification of protein is an arduous but fruitful task. Many chemical methods have been developed for such purpose by carefully balancing reactivity and selectivity. Now both chemists and biologists have in hand an arsenal of tools from which they can select a relevant reaction to tackle their problems. This review focuses on the various chemical transformations available for selective modification of proteins. It also provides a brief overview of some of their main applications, including detection of protein interactions, preparation of bioconjugates, and protein microarrays.
20. MreB drives de novo rod morphogenesis in Caulobacter crescentus via remodeling of the cell wall
Constantin N. Takacs, Sebastian Poggio, Godefroid Charbon, Mathieu Pucheault, Waldemar Vollmer, Christine Jacobs-Wagner
Journal of Bacteriology 2010, 192, 1671-1684.
MreB, the bacterial actin-like cytoskeleton, is required for the rod morphology of many bacterial species. Disruption of MreB function results in loss of rod morphology and cell rounding. Here, we show that the widely used MreB inhibitor A22 causes MreB-independent growth inhibition that varies with the drug concentration, culture medium conditions, and bacterial species tested. MP265, an A22 structural analog, is less toxic than A22 for growth yet equally efficient for disrupting the MreB cytoskeleton. The action of A22 and MP265 is enhanced by basic pH of the culture medium. Using this knowledge and the rapid reversibility of drug action, we examined the restoration of rod shape in lemon-shaped Caulobacter crescentus cells pretreated with MP265 or A22 under nontoxic conditions. We found that reversible restoration of MreB function after drug removal causes extensive morphological changes including a remarkable cell thinning accompanied with elongation, cell branching, and shedding of outer membrane vesicles. We also thoroughly characterized the composition of C. crescentus peptidoglycan by high-performance liquid chromatography and mass spectrometry and showed that MreB disruption and recovery of rod shape following restoration of MreB function are accompanied by considerable changes in composition. Our results provide insight into MreB function in peptidoglycan remodeling and rod shape morphogenesis and suggest that MreB promotes the transglycosylase activity of penicillin-binding proteins.
19. Towards an efficient microsystem for the real-time detection and quantification of mercury in water based on a specifically designed fluorogenic binary task specific ionic liquid
Faïdjiba Loe-Mie, Gilles Marchand, Jean Berthier, Nicolas Sarrut, Mathieu Pucheault, Mireille Blanchard-Desce, Françoise Vinet , Michel Vaultier
Angewandte Chemie International Edition, 2010, 424-427
A microdevice for liquid–liquid extraction and sensing of mercury ions in water uses an ionic liquid containing a task‐specific ionic fluorogenic salt (L1) as the extracting liquid phase. The “off–on” sensing response decreases the likelihood of false positives and allows detection of Hg2+ in aqueous solution down to 50 ppb.
18. Chapitre de Livre : Liquides Ioniques
Mathieu Pucheault, Michel Vaultier
Green Process Engeneering Dunod 2010.
Prix Roberval 2011
17. Review : Task Specific Ionic Liquids and Task Specific Onium Salts
Mathieu Pucheault, Michel Vaultier
Topics in Current Chemistry 2009, 290, 83-126
Task specific ionic liquids (TSILs), or more generally task specific onium salts (TSOSs), can be defined as an association of a cation and anion, one at least being organic, to which has covalently been attached through a linker a function that confers the assembly a specific task. After presentation of the general concept of TSILs and TSOSs, the different methods of preparation of these compounds are developed. Regarding their applications in chemistry, TSILs and TSOSs can be used as soluble supports for reagents and catalysts in multiphasic reactions, enabling high activity and easy recovery of the supported agent. However, additionally, they can be used as soluble supports for organic synthesis in a similar manner to resins and offer several advantages over traditional methods.
16. Organic-Inorganic Hybrid Materials for Enantioselective Organocatalysis
Vivek Srivastava, Kevin Gaubert, Mathieu Pucheault, Michel Vaultier
ChemCatChem, 2009, 1, 94-98.
Chiral organic–inorganic hybrid materials based on amino acid‐exchanged clays are prepared and used for heterogeneous asymmetric organocatalysis. Co‐inclusion of ammonium cations within interlayers greatly enhances yields and selectivities. Recyclability of the material is evaluated, showing no decrease in enantioselectivity or conversion after ten cycles.
15. Sels d’onium et leur utilisation pour la detection et le dosage des metaux
Gilles Marchand, Faidjiba Loe-Mie, Mathieu Pucheault, Mireille Blanchard-Desce, Michel Vaultier
EP2112138, 21/04/2008
14. Targeted Intracellular Protein Degradation Induced by a Small Molecule: En Route to Chemical Proteomics
Ashley R. Schneekloth, Mathieu Pucheault, Hyun Seop Tae, Craig M. Crews
Bioorganic & Medicinal Chemistry Letters 2008, 18, 5904-5909
We have developed a heterobifunctional all-small molecule PROTAC (PROteolysis TArgeting Chimera) capable of inducing proteasomal degradation of the androgen receptor. This cell permeable PROTAC consists of a non-steroidal androgen receptor ligand (SARM) and the MDM2 ligand known as nutlin, connected by a PEG-based linker. The SARM–nutlin PROTAC recruits the androgen receptor to MDM2, which functions as an E3 ubiquitin ligase. This leads to the ubiquitination of the androgen receptor, and its subsequent degradation by the proteasome. Upon treatment of HeLa cells with 10 μM PROTAC for 7 h, we were able to observe a decrease in androgen receptor levels. This degradation is proteasome dependent, as it is mitigated in cells pre-treated with 10 μM epoxomicin, a specific proteasome inhibitor. These results have implications for the potential study and treatment of various cancers with increased androgen receptor levels.
13. Review : Natural products: chemical instruments to apprehend biological symphony
Mathieu Pucheault
Organic and Biomolecular Chemistry 2008, 424-432
As a striking variety of biological activities are elicited by natural products, these chemicals have been used for decades to study biological phenomena. Understanding how these products interfere with normal cell functions at a molecular level led to a wide range of discoveries including new signaling pathways and proteins . Moreover, as natural products often act as chemical inhibitors, such studies often allow the identification of their binding partners as relevant targets for drug design. This article aims to emphasize how natural products or engineered analogs can be used as chemical tools to apprehend some biological problems from the point of view of a chemical biologist.
12. Onium Salt Supported Organic Synthesis in water : application to Grieco’s multicomponent reaction
Aziz Ouach, Said Gmouh, Mathieu Pucheault and Michel Vaultier
Tetrahedron 2008, 64, 1962-1970 .
By using an ammonium chloride salt as water solubilizing moiety, our onium salt supported organic synthesis strategy was extended to water as a solvent. This method allows for high loading capacities both of the supports and their solutions owing to low molecular weight of the onium salts and simplified purification steps as well.
11. Onium Salt Supported Organic Synthesis in Water: Application to Ugi’s 4-Components Reaction
Aziz Ouach, Mathieu Pucheault and Michel Vaultier
Heterocycles 2007, 73, 461-467
The utilization of the Onium Salt Supported Organic Synthesis methodology for Ugi’s 4 components reaction in water is presented. An easy preparation of substrates followed by quantitative reactions led to peptidic moieties which are subsequently easily isolated in good yields and purities. Advantages of the OSSOS strategy including extreme simplification of purification and monitoring of the reaction are presented.
10. Task Specific Onium Salts and Ionic liquids as Soluble Supports in Grieco’s Multicomponent Synthesis of tetrahydroquinolines
Fatima Hassine, Said Gmouh, Mathieu Pucheault and Michel Vaultier
Monaschefte für Chemie 2007, 1167-1174.
In this work was presented an application of the use of task specific onium salts (TSOSs) as soluble supports in Grieco’s multicomponent synthesis of tetrahydroquinolines. These soluble supports are of wide applicability and combine advantages of solid phase synthesis without its limitations with those of solution phase chemistry. After a simple washing step, products were cleaved from the supports and obtained in pure form and good yields.
9. Task Specific Onium Salts (TSOSs) as efficient soluble supports for Zard radical addition to olefins
Julien Verron, Jean-Michel Joerger, Mathieu Pucheault and Michel Vaultier
Tetrahedron Letters 2007, 4055-4057
Task specific onium salts (TSOSs), that is, functionalised ammonium salts, have been used as soluble supports to carry out intermolecular radical additions of xanthates to olefins and functional group interconversions. This methodology provides results by far superior to those reported with other soluble supports and allows for very easy purifications of reaction products.
8. Construction of highly substituted stereodefined dienes via cross-coupling of alpha-allenic acetate
John S. Schneekloth, Jr., Mathieu Pucheault, Craig M. Crews
European Journal of Organic Chemistry 2007, 40-43.
The assembly of highly substituted dienes remains a challenge for organic chemistry. This work represents a strategyfor the construction of highly substituted 1,3‐dienes by meansof a Tsuji–Trost cross coupling between α‐allenic acetates and organozinc reagents. The reaction is high yielding, and installs a trisubstituted olefin with E/Zselectivities up to 95:5 favoring the (E) product. A cheap, commercially available palladium precatalyst and a ligand are used to control theE/Z selectivity. Furthermore, an interesting reversal in selectivity is noted in which appropriate choice of ligand may be used to control the outcome of the reaction and favor the (Z) product. Thirteen examples are described, highlighting the substrate scope of the reaction. It is hoped that the straightforward reaction conditions and high selectivity will make this reaction of broad use in natural product chemistry.
7. Carbinol derivatives via rhodium-catalyzed addition of potassium trifluoro(organo)borates
Mathieu Pucheault, Sylvain Darses, Jean-Pierre Genet
Chemical Communication 2005, 4714-4716
Reaction of potassium aryltrifluoroborates with aldehydes, in the presence of a rhodium catalyst, afforded carbinol derivatives in high yields under mild aqueous conditions; this efficient reaction proved to be general, allowing the production of highly hindered diarylmethanols and aliphatic aldehydes were also reactive under these conditions.
6. Potassium trifluoro(organo)borates in rhodium-catalyzed 1,4-additions to alpha,beta-unsaturated esters
Laure Navarre, Mathieu Pucheault, Sylvain Darses, Jean-Pierre Genêt
Tetrahedron Letters 2005, 127, 4247-4250
This letter describes an efficient and enantioselective conjugate addition of highly stable potassium trifluoro(organo)borates to α,β-unsaturated esters. This reaction, catalyzed by chiral rhodium(I) complexes, affords Michael adducts with high yields and enantiomeric excesses up to 96%
5. Direct access to ketones from aldehydes via rhodium-catalyzed cross-coupling reaction with potassium trifluoro(organo)borates
Mathieu Pucheault, Sylvain Darses, Jean-Pierre Genêt
J. Am. Chem. Soc, 2004, 126, 15356-15357
A direct cross-coupling reaction of aromatic aldehydes with potassium trifluoro(organo)borates afforded ketones in high yields and under mild conditions in the presence of a rhodium catalyst and acetone. This new reaction, involving a formal aldehyde C−H bond activation, is believed to proceed via a Heck-type mechanism followed by hydride transfer to acetone.
4. Efficient access to b-arylamides via asymmetric 1,4-additions of potassium trifluoro(organo)borates
Mathieu Pucheault, Valérie Michaut, Sylvain Darses, Jean-Pierre Genêt
Tetrahedron Lett. 2004, 45, 4729-4732
This paper describes an efficient enantioselective conjugate addition of highly stable potassium trifluoro(organo)borates to α,β-unsaturated amides. This reaction, catalyzed by chiral rhodium(I) complexes affords Michael adducts with high yields and enantiomeric excesses up to 95%.
3. Potassium organotrifluoroborates: new partners in catalytic enantioselective conjugate additions to enones
Mathieu Pucheault, Sylvain Darses, Jean-Pierre Genêt
Tetrahedron Lett. 2002, 43, 6155-6157.
Potassium organotrifluoroborates, highly stable organoboron derivatives and easily accessible from organolithiated reagents, can achieve rhodium(I)-catalyzed asymmetric 1,4-additions to enones using binap as chiral ligand. This reaction proceeds in nearly quantitative yields to afford β-functionalized ketones with e.e. up to 98%.
2. Potassium organotrifluoroborates in rhodium-catalyzed asymmetric 1,4-additions to enones
Mathieu Pucheault, Sylvain Darses, Jean-Pierre Genêt
Eur. J. Org. Chem. 2002, 3552-3557
Potassium organotrifluoroborates, highly stable organoboron derivatives, participate in asymmetric 1,4‐additions to enones. This reaction, catalyzed by cationic rhodium(I) complexes chelated with binap, MeO‐biphep or josiphos ligand, affords 1,4‐adducts with high yields and enantioselectivities of up to 99%. Careful study of the reaction parameters shows the high sensitivity of the reaction to temperature, solvent and the amount of water cosolvent.
1. Efficient access to perfluoroalkylated aryl compounds by Heck reaction
Sylvain Darses, Mathieu Pucheault, Jean-Pierre Genêt
Eur. J. Org. Chem. 2001, 1121-1128
Efficient introduction of perfluorinated tails onto aromatic rings has been achieved by Heck reaction between perfluoroalkenes and arenediazonium salts, catalysed by palladium acetate. Subsequent transition metal catalysed hydrogenation of the double bond afforded a large variety of aromatic compounds bearing an affinity for fluorous solvents. Formation of perfluoroalkylated phosphane ligands and their use in palladium‐catalysed coupling between potassium trifluoro(vinyl)borates and diazonium salts is also described, allowing an easy separation and recycling of the catalytic system