Source: http://ipcm.fr/article639.html?lang=fr
Timestamp: 2019-04-18 18:18:21+00:00

Document:
V. N. Bochatay, F. Chemla, F. Ferreira, O. Jackowski, et A. Pérez-Luna, « β‐Amino Propargylic Fluorides through Stereoselective Electrophilic Fluorodesilylation of 4‐Amino‐1‐allenylsilanes - Bochatay - 2018 - European Journal of Organic Chemistry - Wiley Online Library », European Journal of Organic Chemistry, p. 3862, 2018.
Mots-clés : POLE 1, ROCS.
K. de la Vega-Hernández, E. Romain, A. Coffinet, K. Bijouard, G. Gontard, F. Chemla, F. Ferreira, O. Jackowski, et A. Perez-Luna, « Radical Germylzincation of α-Heteroatom-Substituted Alkynes », Journal of the American Chemical Society, vol. 140, nᵒ 50, p. 17632-17642, déc. 2018.
Résumé : The regio- and stereoselective addition of germanium and zinc across the C–C triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal and internal alkynes is achieved by reaction with a combination of R3GeH and Et2Zn. Diagnostic experiments support a radical-chain mechanism and the β-zincated vinylgermanes that show exceptional stability are characterized by NMR spectroscopy and X-ray crystallography. The unique feature of this new radical germylzincation reaction is that the C(sp2)–Zn bond formed remains available for subsequent in situ Cu(I)- or Pd(0)-mediated C–C or C–heteroatom bond formation with retention of the double bond geometry. These protocols offer modular access to elaborated tri- and tetrasubstituted vinylgermanes decorated with heteroatom substituents β to germanium that are useful for the preparation of stereodefined alkenes.
R. Maazaoui, R. Abderrahim, F. Chemla, F. Ferreira, A. Perez-Luna, et O. Jackowski, « Catalytic Chemoselective and Stereoselective Semihydrogenation of Alkynes to E-Alkenes Using the Combination of Pd Catalyst and ZnI2 », Organic Letters, vol. 20, nᵒ 23, p. 7544-7549, déc. 2018.
Résumé : An efficient E-selective semihydrogenation of internal alkynes was developed under low dihydrogen pressure and low reaction temperature from commercially available reagents: Cl2Pd(PPh3)2, Zn0, and ZnI2. Kinetic studies and control experiments underline the significant role of ZnI2 in this process under H2 atmosphere, establishing that the transformation involves syn-hydrogenation followed by isomerization. This simple and easy-to-handle system provides a route to E-alkenes under mild conditions.
R. K. Nandi, A. Perez‐Luna, D. Gori, R. Beaud, R. Guillot, C. Kouklovsky, V. Gandon, et G. Vincent, « Triflic Acid as an Efficient Brønsted Acid Promoter for the Umpolung of N‐Ac Indoles in Hydroarylation Reactions », Advanced Synthesis & Catalysis, vol. 360, nᵒ 1, p. 161-172, janv. 2018.
F. Roudesly, L. F. Veiros, J. Oble, et G. Poli, « Pd-Catalyzed Direct C–H Alkenylation and Allylation of Azine N-Oxides », Organic Letters, vol. 20, nᵒ 8, p. 2346-2350, avr. 2018.
Résumé : A Pd-catalyzed direct C2-alkenylation of azine N-oxides with allyl acetate is disclosed. The products are formed through an allylation/isomerization cascade process. The use of a tri-tert-butylphosphonium salt as the ligand precursor and KF is mandatory for optimal yields. When cinnamyl acetate is used, the same catalytic system promotes C2-cinnamylation of the azine N-oxide without subsequent isomerization. A mechanism is proposed on the basis of experimental studies and DFT calculations.
R. Beaud, R. K. Nandi, A. Perez-Luna, R. Guillot, D. Gori, C. Kouklovsky, N. - E. Ghermani, V. Gandon, et G. Vincent, « Revealing the electrophilicity of N-Ac indoles with FeCl3: a mechanistic study », Chemical Communications, vol. 53, nᵒ 43, p. 5834-5837.
Résumé : Herein, we report a mechanistic exploration of the unusual FeCl3-mediated hydroarylation of N-Ac indoles. Electron density topology analysis of a crystal, in situ IR monitoring, Hammett and Taft studies as well as DFT computations allowed us to determine that activation of acetyl with FeCl3 and of the C2C3 bond with a proton is involved.
M. Beaupérin, D. Polat, F. Roudesly, S. Top, A. Vessières, J. Oble, G. Jaouen, et G. Poli, « Approach to ferrocenyl-podophyllotoxin analogs and their evaluation as anti-tumor agents », Journal of Organometallic Chemistry, vol. 839, p. 83-90.
Résumé : Podophyllotoxin is a natural product endowed of a high antimitotic activity and a high affinity for tubulin. Its action results in the cessation of cell division, inducing cell death. However, its high toxicity restrains its use as drug. To overcome this drawback, several chemical modifications of the native podophyllotoxin have been made. However, to date, no reports have so far been directed toward incorporation of a metallocene moiety. The search for new organometallic drugs is a central field in drug discovery, including the domain of cancer therapy. In particular, metallocenyl moieties are known to increase or decrease, depending on the degree of conjugation in the organometallic motif, the selectivity of drugs toward cancer cells. The conjugate organometallic compound reduces the damage of healthy tissues, yet permitting the selective desired antimitotic and cytotoxic effects of the active principle. We report here the synthesis of ferrocene-containing podophyllotoxin analogs and preliminary antiproliferative tests.
Mots-clés : Antitumor agent, Bioorganometallic chemistry, CHEMBIO, Ferrocene, Multi-step synthesis, Palladium, Podophyllotoxin, POLE 1, POLE 3, ROCS.
V. N. Bochatay, L. Debien, F. Chemla, F. Ferreira, O. Jackowski, et A. Perez-Luna, « Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides and acetylenic aziridines », Comptes Rendus Chimie, vol. 20, nᵒ 6, p. 609-616.
Résumé : Lithium alkynyl(disilyl)zincates obtained from metalated ethynyloxiranes, as well as from N-tert-butanesulfinyl(ethynyl)aziridines or N-tert-butanesulfonyl(ethynyl)aziridines, undergo 1,2-migration of the organosilyl group with ring opening of the oxirane or aziridine ring by SNi displacement. A developed protocol that involves nBuLi for the metalation step offers a straightforward approach to the corresponding δ-oxy- and δ-amino α-silyl allenylzinc intermediates. The reagents derived from the epoxides are amenable to subsequent in situ condensation with aldehydes or ketones to provide 1,3-diols but not those derived from aziridines that only react sluggishly in similar condensations.
Mots-clés : alkynes, carbenoids, POLE 1, rearrangement, ROCS, silicon, Zinc.
T. Borelli, S. Brenna, G. Broggini, J. Oble, et G. Poli, « (Diacyloxyiodo)benzenes-Driven Palladium-Catalyzed Cyclizations of Unsaturated N-Sulfonylamides: Opportunities of Path Selection », Advanced Synthesis & Catalysis, vol. 359, nᵒ 4, p. 623-628.
Résumé : A study of the palladium(II)-catalyzed cyclization of unsaturated N-sulfonylamides was undertaken, using (diacyloxyiodo)benzenes as terminal oxidizing agents. Different reactivities were observed as a function of the nature of the unsaturation (terminal vs. internal), or of the hypervalent iodine compound used (diacetoxyiodobenzene vs. bistrifluoroacetoxyiodobenzene). Proper parameter selection allows the direction of the cyclization to be chosen towards either a global aminoacetoxylation, an allylic amination via aminopalladation, or an allylic amination via allylic C–H activation.
Mots-clés : allylic compounds, amination, C–H activation, homogeneous catalysis, Palladium, POLE 1, ROCS.
G. Bouhalleb, O. Mhasni, G. Poli, et F. Rezgui, « Direct palladium-catalyzed allylic alkylations of alcohols with enamines: Synthesis of homoallyl ketones », Tetrahedron Letters, vol. 58, p. 2525-2529.
Résumé : An efficient, direct nucleophilic allylic substitution of α-, β- and γ-substituted alcohols with enamines, using the Pd(OAc)2/PPh3 catalyst system and ZnBr2 as a promoter in CH2Cl2 at reflux, is reported. The reaction course was dependent on the steric hindrance at the α- or γ-positions with respect to the functionalized α-carbon, selectively affording in moderate to good yields, α- or γ-homoallyl ketones, the so-called “linear” and “branched” products, respectively.
Mots-clés : Allylic alcohol, Allylic substitution, Enamine, Homoallyl ketone, Palladium, POLE 1, ROCS.
C. Fopp, K. Isaac, E. Romain, F. Chemla, F. Ferreira, O. Jackowski, M. Oestreich, et A. Perez-Luna, « Stereodivergent Synthesis of β-Heteroatom-Substituted Vinyl­silanes by Sequential Silylzincation–Copper(I)-Mediated Electrophilic­ Substitution », Synthesis, vol. 49, nᵒ 04, p. 724-735.
Z. Mao, E. Martini, G. Prestat, J. Oble, P. - Q. Huang, et G. Poli, « Analogues of the 2-carboxyl-6-hydroxyoctahydroindole (CHOI) unit from diverging Pd-catalyzed allylations: Selectivity as a function of the double bond position », Tetrahedron Letters, vol. 58, nᵒ 44, p. 4174-4178, nov. 2017.
Résumé : Pd-catalyzed allylations of cyclic bis-allylic substrates, carried out either as two separate steps or in a pseudo-domino fashion, can generate 2-carboxyl-hexahydroindoles bearing an unsaturation in different positions. Sequential homologation, and epoxidation or syn-dihydroxylation steps were investigated to access analogues of the bicyclic 2-carboxyl-6-hydroxyoctahydroindole motif of aeruginosins, a family of peptides displaying serine protease inhibitor activity.
Mots-clés : Allylic substitution, CHOI core, Domino reaction, Palladium catalysis, POLE 1, ROCS.
C. Pezzetta, L. F. Veiros, J. Oble, et G. Poli, « Murai Reaction on Furfural Derivatives Enabled by Removable N,N′-Bidentate Directing Groups », Chemistry - A European Journal, vol. 23, p. 8385-8389.
Résumé : Furfural and related compounds are industrially relevant building blocks obtained from lignocellulosic biomass. To enhance the added value of these renewable resources, a Ru-catalyzed hydrofurylation of alkenes, involving a directed C−H activation at C3 of the furan ring, was developed. A thorough experimental study revealed that a bidentate amino-imine directing group enabled the desired coupling. Removal of the directing group occurred during the purification step, directly releasing the C3-functionalized furfurals. Development of the reaction as well as optimization and scope of the method were described. A mechanism was proposed on the basis of DFT calculations.
Mots-clés : aldimines, alkenes, C−H activation, furfural, POLE 1, ROCS, Ruthenium.
F. Roudesly, J. Oble, et G. Poli, « Metal-catalyzed CH activation/functionalization: The fundamentals », Journal of Molecular Catalysis A: Chemical, vol. 426, Part B, p. 275-296.
Résumé : An isolated CH bond in a molecule has a very low reactivity owing to the large kinetic barrier associated to the CH bond cleavage and the apolar nature of this bond. For this reason, the selective reactivity of such a non-functional group is under active study since several decades and is still regarded as the Holy Grail in chemistry. Metal-catalyzed CH activation/functionalization chemistry allows the step-economical and original construction of CC as well as CO and CN bonds starting from hydrocarbons (or hydrocarbon fragments) without the need of prior non catalytic oxidation steps. Furthermore, it can be of utmost importance in the domain of multistep syntheses, and also in transformations of societal significance such as the conversion of methane into methanol. This tutorial review addresses to students and researchers who would like to become acquainted with this fascinating topic. After a brief historical introduction, the main mechanistic fundaments of metal-catalyzed CH activation are exposed. Then, a selection of seminal advances and conceptual breakthroughs are presented.
Mots-clés : C-heteroatom bond formation, CC bond formation, CH activation, CH functionalization, Mechanistic study, POLE 1, ROCS.
I. Zelocualtecatl-Montiel, F. García-Álvarez, J. R. Juárez, L. Orea, D. Gnecco, A. Mendoza, F. Chemla, F. Ferreira, O. Jackowski, D. M. Aparicio, A. Perez-Luna, et J. L. Terán, « Asymmetric Tandem Conjugate Addition–Aldol Condensation with N-Acryloyloxazolidines Derived from 2-Phenylglycinol », Asian Journal of Organic Chemistry, vol. 6, nᵒ 1, p. 67-70.
chiral enantiopure oxazolidines derived from 2-phenylglycinol, and carbonyl compounds is disclosed. The reaction proceeds through a radical-polar crossover mechanism involving the aldol condensation of a trisubstituted zinc enolate through a Zimmerman–Traxler transition state. Installation of a 2-pyridine moiety at the hemiaminal position of the chiral auxiliary allows obtaining both excellent asymmetric induction and diastereoselectivity (up to >90 % de). The developed protocol is suitable for aromatic and aliphatic aldehydes, as well as ketones.
Mots-clés : aldol reaction, chiral oxazolidines, Diastereoselectivity, domino reactions, POLE 1, radical-polar mechanism, ROCS.
V. N. Bochatay, Z. Neouchy, F. Chemla, F. Ferreira, O. Jackowski, et A. Pérez-Luna, « 4-Amino-1-allenylsilanes from 4-Aminopropargylic Acetates through a Silylzincation/Elimination Sequence », Synthesis, vol. 48, nᵒ 19, p. 3287-3300.
D. Diamante, S. Gabrieli, T. Benincori, G. Broggini, J. Oble, et G. Poli, « Dehydrogenative Allylic Aminations of But-3-enoic Acid Derivatives », Synthesis, vol. 48, nᵒ 19, p. 3400-3412.
F. J. S. Duarte, G. Poli, et M. J. Calhorda, « Mechanistic Study of the Direct Intramolecular Allylic Amination Reaction Catalyzed by Palladium(II) », ACS Catalysis, vol. 6, nᵒ 3, p. 1772-1784.
Résumé : DFT calculations (PBE1PBE/6-31G(d,p), Def2-TZVPPD) were performed to study the intramolecular C–H amination of an unsaturated carbamate catalyzed by [Pd(LL)(OAc)2] (2), where LL is the bis(sulfoxide) ligand PhS(O)(CH2)2S(O)Ph. The coordination takes place by an associative path over a trigonal-bipyramidal transition state. The LL ligand undergoes a coordination shift from κ2S,S to κ1S, leaving an open position for binding of the substrate (C═C). In the next step, the C–H activation, the transition state for the hydrogen abstraction from the substrate to form the σ-allyl complex has an energy of 124.0 kJ mol–1, which is the highest energy in the whole mechanism (TOF-determining transition state). The σ-allyl converts easily in the π-allyl, the acetic acid molecule leaving the coordination sphere. The remaining acetate receives the second hydrogen from the NH group, while the newly formed acetic acid molecule is replaced by the pendant arm of the LL ligand, and the cyclization takes place (nucleophilic attack). During these changes, the metal is reduced to Pd(0) in the form of the Pd(0) complex of the oxazolidinone product, the most stable species in the cycle (TOF-determining intermediate). Either the C–H activation or the Pd(0) oxidation may be the step determining the energy span of the reaction, depending on reaction conditions.
B. J. Fallon, V. Corcé, M. Amatore, C. Aubert, F. Chemla, F. Ferreira, A. Perez-Luna, et M. Petit, « A well-defined low-valent cobalt catalyst Co(PMe3)4 with dimethylzinc: a simple catalytic approach for the reductive dimerization of benzyl halides », New Journal of Chemistry, vol. 40, nᵒ 12, p. 9912-9916.
Résumé : Herein, we report the first catalytic version of a cobalt-catalysed reductive homocoupling of benzyl halides which proceeds with low catalyst loadings (0.5 to 5 mol%). By synthetizing each cobalt intermediate we demonstrate that reaction proceeds through two single electron transfers (SET) and that dimethylzinc is only involved in the regeneration of the catalytic species.
Mots-clés : MACO, POLE 1, ROCS.
B. J. Fallon, E. Derat, M. Amatore, C. Aubert, F. Chemla, F. Ferreira, A. Perez-Luna, et M. Petit, « C2-Alkylation and Alkenylation of Indoles Catalyzed by a Low-Valent Cobalt Complex in the Absence of Reductant », Organic Letters, vol. 18, nᵒ 9, p. 2292-2295.
Résumé : Herein an extremely versatile, well-defined, low-valent cobalt catalyst [Co(PMe3)4] capable of intermolecular and intramolecular imine-directed C2-alkylation and alkenylation of indoles is reported. The reaction proceeds in the absence of reducing agents or additives, affording a range of substituted indoles and dihydropyrroloindoles in high yields and regioselectivities. With the aid of deuterium labeling studies and DFT (Density Functional Theory) calculations, a mechanism is proposed that is based on a Ligand-to-Ligand Hydrogen Transfer pathway.
C. Fopp, E. Romain, K. Isaac, F. Chemla, F. Ferreira, O. Jackowski, M. Oestreich, et A. Perez-Luna, « Stereodivergent Silylzincation of α-Heteroatom-Substituted Alkynes », Organic Letters, vol. 18, nᵒ 9, p. 2054-2057.
Résumé : Zinc reagents (Me2PhSi)2Zn and [(Me3Si)3Si]2Zn undergo highly regio- and stereoselective addition across the carbon–carbon triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal alkynes in the absence of copper or any other catalyst. Both reagents yield exclusively β-isomers, and the stereoselectivity is determined by the silyl group: Me2PhSi for cis or (Me3Si)3Si for trans. These stereodivergent silylzincation protocols offer an efficient access to heteroatom-substituted vinylsilanes with either double bond geometry, including trisubstituted vinylsilanes by one-pot electrophilic substitution of the intermediate C(sp2)–Zn bond by copper(I)-mediated carbon–carbon bond formation.
D. Lebœuf, L. Marin, B. Michelet, A. Perez-Luna, R. Guillot, E. Schulz, et V. Gandon, « Harnessing the Lewis Acidity of HFIP through its Cooperation with a Calcium(II) Salt: Application to the Aza-Piancatelli Reaction », Chemistry - A European Journal, vol. 22, nᵒ 45, p. 16165-16171.
Résumé : A method to extend the scope of the aza-Piancatelli reaction between 2-furylcarbinols and anilines is depicted. We found that 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) is the solvent of choice for this transformation, as it outcompetes the usual solvents in terms of rate and yield. Side reactions and other issues raised by the title reaction are prevented, thereby providing an avenue to complex molecules that were previously inaccessible. Lewis acidity studies and computations were carried out to unveil the role of HFIP. Based on these results, we propose that HFIP is, in fact, acting as a Lewis acid and that its acidity can be enhanced when combined with a calcium(II) salt.
Mots-clés : alcohol, Calcium, cooperative catalysis, density functional calculations, electrocyclic reactions, POLE 1, ROCS.
M. M. Lorion, F. J. S. Duarte, M. J. Calhorda, J. Oble, et G. Poli, « Opening the Way to Catalytic Aminopalladation/Proxicyclic Dehydropalladation: Access to Methylidene γ-Lactams », Organic Letters, vol. 18, nᵒ 5, p. 1020-1023.
Résumé : A new aerobic intramolecular palladium(II)-based catalytic system that triggers aminopalladation/dehydropalladation of N-sulfonylalkenylamides to give the corresponding methylidene γ-lactams has been identified. Use of triphenylphosphine and chloride anion as ligands is mandatory for optimal yields, and molecular oxygen can be used as the sole terminal oxidant. Scope and limitations of the methods are described. A mechanism is proposed on the basis of experimental results as well as density functional theory calculations.
M. M. Lorion, C. Kammerer, G. Prestat, et G. Poli, « Sequential Pd-catalyzed allylic alkylation / Ru-catalyzed ring-closing metathesis, », in Comprehensive Organic Chemistry Experiments for the Laboratory Classroom, C. A. M. Afonso, N. R. Candeias, D. P. Simao, A. F. Trindade, J. A. S. Coelho, et B. Tan, Éd. Royal Society of Chemistry Press, p. 650-655.
Résumé : This expansive and practical textbook contains organic chemistry experiments for teaching in the laboratory at the undergraduate level covering a range of functional group transformations and key organic reactions.The editorial team have collected contributions from around the world and standardized them for publication. Each experiment will explore a modern chemistry scenario, such as: sustainable chemistry; application in the pharmaceutical industry; catalysis and material sciences, to name a few. All the experiments will be complemented with a set of questions to challenge the students and a section for the instructors, concerning the results obtained and advice on getting the best outcome from the experiment. A section covering practical aspects with tips and advice for the instructors, together with the results obtained in the laboratory by students, has been compiled for each experiment.Targeted at professors and lecturers in chemistry, this useful text will provide up to date experiments putting the science into context for the students.
M. M. Lorion, J. Oble, et G. Poli, « Palladium catalyzed oxidative aminations and oxylations: where are we? », Pure and Applied Chemistry, vol. 88, nᵒ 4, p. 381–389.
Résumé : Selective product formation in the Pd-catalyzed cyclization of unsaturated amide and carboxylic acid derivatives is an intriguing and challenging task. We recently discovered that the oxidative intramo-lecular Pd(II)-catalyzed amination or oxylation of unsaturated N-sulfonyl carbamates, N-sulfonyl carbox-amides and carboxylic acids takes place through the involvement of cyclic (usually, 5-or 6-membered) aminopalladated (AmPIs) or oxypalladated (OxPI) intermediates. Such cyclic intermediates can undergo a variety of transformations such as distocyclic β-H elimination, oxidative acetoxylation or intramolecular car-bopalladation, depending upon the substrate and/or the reaction conditions. In the absence of appropriate reaction pathways, the cyclic nucleopalladated intermediates (NuPIs) simply engage in an inconsequential equilibrium with the initial substrate and other transformations occur such as allylic C–H activation or, in the particular case of allyl carbamates, [3,3]-sigmatropic rearrangement.
R. Maazaoui, M. Pin-Nó, K. Gervais, R. Abderrahim, F. Ferreira, A. Perez-Luna, F. Chemla, et O. Jackowski, « Domino Methylenation/Hydrogenation of Aldehydes and Ketones by Combining Matsubara's Reagent and Wilkinson's Catalyst », European Journal of Organic Chemistry, p. 5732-5737.
Résumé : The methylenation/hydrogenation cascade reaction of aldehydes or ketones through a domino process involving two ensuing steps in a single pot is realized. The compatibility of Matsubara's reagent and Wilkinson's complex give a combination that allows, under dihydrogen, the transformation of a carbonyl function into a methyl group. This new method is suitable to introduce an ethyl motif from aromatic and aliphatic aldehydes with total chemoselectivity and total retention of α-stereochemical purity. The developed procedure is also extended to the introduction of methyl groups from ketones.
Mots-clés : aldehydes, chemoselectivity, domino reactions, hydrogenation, ketones, Methylenation, POLE 1, ROCS.
R. Piccardi, L. Micouin, et O. Jackowski, « The Chemistry of Alkynylaluminum Species », in PATAI'S Chemistry of Functional Groups, I. Marek, Éd. John Wiley & Sons, Ltd, p. 1-47.
Résumé : Among organoaluminum reagents, alkynylaluminum species exhibit peculiar physicochemical properties and reactivity. Depending on the nature of easily controlled parameters such as substituents on the aluminum center or additives and solvent, their Lewis acidity and nucleophilicity can be independently fine-tuned in a very precise manner. This chapter describes the preparation of alkynylaluminum compounds, their structure, and their reactivity in several synthetic transformations involving the transfer of their alkynyl group such as nucleophilic substitution reactions, additions to C–X multiple bonds, epoxide and aziridine ring-opening reactions, reactions with oxonium and iminium species, metal-assisted cross-coupling reactions, as well as in rearrangements. The reactivity of the triple bond of these reagents is also presented.
Mots-clés : acetylides, alanates, alanes, alkynylaluminum, Lewis acidity, POLE 1, ROCS, triethylaluminum, trimethylaluminum.
J. Ramirez Hernandez, F. Chemla, F. Ferreira, O. Jackowski, J. Oble, A. Perez-Luna, et G. Poli, « tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions », Chimia, vol. 70, nᵒ 1, p. 84-92.
Résumé : The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon–nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions.
Mots-clés : amination, Chiral Nucleophiles, POLE 1, ROCS, Tert-Butanesulfinamide.
R. Beniazza, E. Romain, F. Chemla, F. Ferreira, O. Jackowski, et A. Perez-Luna, « Zinc Radical Transfer Based Modular Approach to Enantiopure Alkylidene-β-Prol­ines from N-(tert-Butylsulfinyl)-α-(aminomethyl)acrylates », European Journal of Organic Chemistry, p. 7661-7665.
Résumé : N-(tert-Butylsulfinyl)-α-(aminomethyl)acrylates with tethered silylated alkynes undergo a tandem 1,4-addition/carbozincation reaction upon exposure to dialkylzinc compounds in the presence of air. The process follows a zinc-radical-transfer mechanism and provides vinylzinc adducts that can react subsequently with electrophiles. High levels of chiral induction (dr > 90:10) from the tert-butylsulfinyl directing group are achieved during the radical 5-exo-dig cyclization by adding samarium(III) triflate. The sequence overall provides straightforward modular access to enantiopure (E)-4-alkylidene-β-prolines from tert-butanesulfinamide.
Mots-clés : Amino acids, cyclization, POLE 1, radicals, ROCS, Synthetic methods, Tandem reactions, Zinc.
V. N. Bochatay, Y. Sanogo, F. Chemla, F. Ferreira, O. Jackowski, et A. Pérez-Luna, « Ring-Opening of N-tert-Butanesulfinylethynylaziridines with Lithium Tris(dimethylphenylsilyl)zincate: Stereoselective Access to 4-Amino-1-allenylsilanes », Advanced Synthesis & Catalysis, vol. 357, nᵒ 13, p. 2809-2814.
Résumé : The ring-opening of N-tert-butanesulfinylethynylaziridines with lithium tris(dimethylphenylsilyl)zincate is reported. The reaction is demonstrated to be both stereoselective and stereospecific and to proceed through an anti-SN2′ process. Further deprotection of the nitrogen atom under mild conditions allows access to 4-amino-1-(dimethylphenylsilyl)allenes with high yields and levels of stereoselectivity.
Mots-clés : allenes, Asymmetric synthesis, aziridines, Diastereoselectivity, POLE 1, ROCS, zincates.
G. Broggini, G. Poli, E. M. Beccalli, F. Brusa, S. Gazzola, et J. Oble, « Ruthenium-Catalyzed Hydroamination of Aminoallenes: an Approach to Vinyl Substituted Heterocycles », Advanced Synthesis & Catalysis, vol. 357, nᵒ 4, p. 677-682.
Résumé : Heterosubstituted aminoallenes underwent smooth ruthenium-catalyzed intramolecular exo-hydroamination reactions yielding the corresponding five-, six-, or seven-membered 1,3-diaza- or 1,3-oxaza-heterocyclic structures. This procedure is a valuable and less expensive alternative to the already known transition metal-catalyzed hydroamination reactions of aminoallenes.
Mots-clés : allenes, heterocycles, homogeneous catalysis, Hydroamination, POLE 1, ROCS, Ruthenium.
B. J. Fallon, E. Derat, M. Amatore, C. Aubert, F. Chemla, F. Ferreira, A. Perez-Luna, et M. Petit, « C–H Activation/Functionalization Catalyzed by Simple, Well-Defined Low-Valent Cobalt Complexes », Journal of the American Chemical Society, vol. 137, nᵒ 7, p. 2448-2451.
Résumé : A facile C?H activation and functionalization of aromatic imines is presented using low-valent cobalt catalysts. Using Co(PMe3)4 as catalyst we have developed an efficient and simple protocol for the C?H/hydroarylation of alkynes with an anti selectivity. Deuterium-labeling experiments, DFT calculations coupled with the use of a well-defined catalyst have for the first time shed light on the elusive black box of cobalt catalyzed C?H functionalization.
F. Louafi, M. M. Lorion, J. Oble, et G. Poli, « Dichotomous Reaction Pathways for the Oxidative Palladium(II)-Catalyzed Intramolecular Acyloxylation of Alkenes », Synlett, vol. 26, nᵒ 16, p. 2237-2242.
F. Chemla, F. Ferreira, O. Jackowski, L. Micouin, et A. Perez-Luna, « Carbon–Carbon Bond Forming Reactions Mediated by Organozinc Reagents », in Metal-Catalyzed Cross-Coupling Reactions and More, A. de Meijere, S. Bräse, et M. Oestreich, Éd. Wiley-VCH Verlag GmbH & Co. KGaA, p. 279-364.
Mots-clés : copper catalyst, functional organozinc reagents, iron catalyst, nickel catalyst, organozinc reagents, palladium catalyst, POLE 1, ROCS, the Negishi cross-coupling reaction, transmetallation.
F. Chemla, F. Ferreira, A. Perez-Luna, L. Micouin, et O. Jackowski, « Carbon–Carbon Bond-Forming Reactions Mediated by Organomagnesium Reagents », in Metal-Catalyzed Cross-Coupling Reactions and More, A. de Meijere, S. Bräse, et M. Oestreich, Éd. Wiley-VCH Verlag GmbH & Co. KGaA, p. 365-422.
Mots-clés : cobalt catalyst, functional organomagnesium reagents, Grignard reagents, iron catalyst, manganese catalyst, nickel catalyst, organomagnesium reagents, oxidative cross-coupling, POLE 1, ROCS.
I. Erray, J. Oble, G. Poli, et F. Rezgui, « Regioselective S-allylation of thiols with cyclic Baylis–Hillman acetates », Journal of Sulfur Chemistry, vol. 35, nᵒ 2, p. 128-136.
Mots-clés : adducts, allyl sulfides, alpha-(nitroalkyl)enones, Baylis-Hillman, carbonates, catalyzed allylic alkylations, conjugate addition, esters, mild, nucleophiles, Nucleophilic substitution, POLE 1, replacement, ROCS, stereoselective-synthesis, sulfides.
I. Erray, F. Rezgui, J. Oble, et G. Poli, « Microwave-Assisted Palladium-Catalyzed Allylation of beta-Enaminones », Synlett, vol. 25, nᵒ 15, p. 2196-2200.
Résumé : A new palladium-catalyzed approach for the C-allylation of beta-enaminones under microwave irradiation is reported. This methodology provides an easy access to a variety of alpha-allylated enaminones. The reaction takes place with the preservation of the enamine function, which is poised for further transformations towards nitrogen-containing heterocycles.
Mots-clés : aldehydes, allyl acetate, Allylation, alpha-allylation, asymmetric allylic alkylation, direct alkenylation, domino sequence, enaminone, indoles, intramolecular heck reaction, microwave irradiation, nonaromatic enamides, Palladium, POLE 1, ROCS, sequential wittig, transition-metal.
C. Kammerer, G. Prestat, D. Madec, et G. Poli, « Synthesis of γ-Lactams and γ-Lactones via Intramolecular Pd-Catalyzed Allylic Alkylations », Accounts of Chemical Research, vol. 47, nᵒ 12, p. 3439-3447.
Résumé : ConspectusLactones and lactams are a well-known class of natural products and can be used as building blocks in organic synthesis. In addition, they can be found in many natural sources and synthetic drugs and have a broad range of biological or odorant properties. Chemists can create these useful compounds through palladium catalysis, which is a highly efficient tool for organic synthesis and is conveniently functional group tolerant. In this Account, we describe our work over the past 15 years in intramolecular Pd-catalyzed allylations where we have tethered the nucleophile and the electrophile by either an amide or an ester moiety, to produce ?-lactams and ?-lactones. We discuss in detail how the nature of the heteroatom tether influences the regioselectivity of the reaction. For example, a ketone [?C(O)CH2?] tether leads to mixtures of 5-exo and 7-endo cyclization products, while ester or amide [?C(O)X?] tethers afford sole 5-exo products. However, in the case of X = O, we were required to overcome two issues in the synthesis of ?-lactones. First of all, the tethering ester function can compete with the allylic leaving group in the oxidative addition to the Pd(0) center. Second, in this case, the proportion of the conformers that have a suitable geometry for cyclization is very low. When we insert a juxtaposed silyl group on the allyl fragment, the molecule can undergo oxidative addition and functionalization of the lactone via Hiyama cross-coupling.We also performed DFT calculations on these systems, which allowed us to better understand the behavior of [?C(O)X?] and [?C(O)CH2?] tethers. Computations also let us rationalize the different reactivities that we observed as a function of the geometry (Z or E) of the starting substrates. In addition, we were able to synthesize natural products or analogs (α-kainic acid, isoretronecanol, and picropodophyllin). We could turn these allylation reactions into asymmetric transformations and incorporate them into domino sequences. Thus, an allylation/Mizoroki?Heck sequence allowed us to straightforwardly access an aza-analog of picropodophyllin, as well as reach the lysergic acid backbone. Finally, we found that through carbopalladation of allenes, we could efficiently synthesize the key ?3-allylpalladium intermediates that were then ready for allylation reactions.
Mots-clés : acid, cyclizations, domino sequence, POLE 1, ROCS, route, silylated pyrrolidones.
F. Liron, J. Oble, M. M. Lorion, et G. Poli, « Direct Allylic Functionalization Through Pd-Catalyzed C-H Activation », European Journal of Organic Chemistry, nᵒ 27, p. 5863-5883, 2014.
Mots-clés : aerobic oxidative amination, Allylation, bond activation, c-h activation, free nonacidic conditions, homogeneous catalysis, hydrocarbon oxidation, molecular-oxygen, multistep electron-transfer, olefin-palladiumchlorid-komplexe, Palladium, POLE 1, POLE 2, Reaction mechanisms, ROCS, serial ligand catalysis, synthetic reactions, terminal olefins.
M. M. Lorion, F. Nahra, V. L. Ly, C. Mealli, A. Messaoudi, F. Liron, J. Oble, et G. Poli, « Digging into the mechanism of oxidative Pd(II)-catalyzed aminations », Chimica Oggi-Chemistry Today, vol. 32, nᵒ 5, p. 30-34.
Résumé : Although the Pd(II)-catalyzed alkene aminopalladation and allylic C-H activation have been much described in literature, the in-depth mechanism of such type of process is far from being a simple matter. This account focuses on the oxidative intramolecular Pd(II)-catalyzed amination of unsaturated N-sulfonyl carbamates and carboxamides, revealing that different mechanistic paths can be operative. In particular, after activation of the unsaturation by Pd(II) catalyst, aminopalladation can take place, affording the corresponding high-energy cyclic (5- or 6-membered) aminopalladated intermediate (AmPI). This latter can evolve along different pathways, such as: distocyclic beta-H elimination, oxidation by a strong terminal oxidant, or carbopalladation. Otherwise, the cyclic AmPI can lay dormant, in equilibrium with the initial substrate. In this case, alternative reactivities may take place, such as allylic C-H activation of the olefinic substrate, [3,3]-sigmatropic rearrangement, or decomposition.
Mots-clés : alkenes, Allylic alkylation, aminopalladation, beta-hydride elimination, c-h activation, c-h alkylation, Catalysis, DFT calculations, dicationic palladium(ii), highly electrophilic site, molecular-oxygen, olefins, organic-synthesis, Palladium, platinum(ii) complexes, POLE 1, ROCS, [3,3]-sigmatropic rearrangement.
L. Mistico, E. Ay, V. Huynh, A. Bourderioux, F. Chemla, F. Ferreira, J. Oble, A. Perez-Luna, G. Poli, et G. Prestat, « Reactivity of tert-butanesulfinamides in palladium-catalyzed allylic substitutions », Journal of Organometallic Chemistry, vol. 760, p. 124-129.
Mots-clés : 1,2-addition, Allylic substitution, alpha-diketones, amination, amines, asymmetric-synthesis, cyclization, Palladium, POLE 1, ROCS, Sulfinamide, sulfur-olefin ligands.
J. Rajabi, M. M. Lorion, V. L. Ly, F. Liron, J. Oble, G. Prestat, et G. Poli, « Dormant versus Evolving Aminopalladated Intermediates: Toward a Unified Mechanistic Scenario in Pd <sup>II</sup> -Catalyzed Aminations », Chemistry - A European Journal, vol. 20, nᵒ 6, p. 1539-1546.
Mots-clés : aerobic oxidative amination, allylic amination, aminopalladation, beta-hydride elimination, c-h activation, c-h alkylation, dicationic palladium(ii), highly electrophilic site, hydrocarbon oxidation, hypervalent iodine reagents, organic-synthesis, Palladium, platinum(ii) complexes, POLE 1, ROCS, terminal olefins, [3,3]-sigmatropic rearrangement.
M. Rigamonti, G. Prestat, G. Broggini, et G. Poli, « Synthesis of 1,4-benzodiazepinones via palladium-catalysed allene carbopalladation/amination domino sequence », Journal of Organometallic Chemistry, vol. 760, p. 149-155.
Résumé : Vinyl-substituted 1,4-benzodiazepinones were obtained in good yields (10 examples, 61–82% yield) via the reaction between N-allenyl anthranyl amides and aryl iodides under Pd(0) catalysis. This new single cycle catalytic domino transformation involves a C–C followed by an N–C bond formation.
Mots-clés : 1,4-Benzodiazepinones, allene, amination, analogs, antagonists, asymmetric-synthesis, carboamination, Carbopalladation, derivatives, domino reactions, gaba(a) receptor, inhibitors, Palladium, POLE 1, potent, pyrrolobenzodiazepines, ROCS, route.
E. Romain, C. Fopp, F. Chemla, F. Ferreira, O. Jackowski, M. Oestreich, et A. Perez-Luna, « Trans-Selective Radical Silylzincation of Ynamides », Angewandte Chemie International Edition, vol. 53, nᵒ 42, p. 11333-11337.
Résumé : The silylzincation of terminal ynamides is achieved through a radical-chain process involving (Me3Si)(3)SiH and R2Zn. A potentially competing polar mechanism is excluded on the basis of diagnostic control experiments. The unique feature of this addition across the CC bond is its trans selectivity. One-pot electrophilic substitution of the Csp2Zn bond by Cu-I-mediated CC bond formation and subsequent manipulation of the Csp2Si bond provides a modular access to Z-,-disubstituted enamides.
Mots-clés : acetylenes, alkenes, carbon multiple bonds, catalyzed silylzincation, Copper, enamides, POLE 1, radical reactions, ROCS, silicon, silylcupration, silylmetalation, stereoselective-synthesis, terminal alkynes, vinylsilanes, Zinc.
C. Caumes, N. Delsuc, R. Beni Azza, I. Correia, F. Chemla, F. Ferreira, L. Carlier, A. Perez Luna, R. Moumné, O. Lequin, et P. Karoyan, « Homooligomers of substituted prolines and β-prolines: syntheses and secondary structure investigation », New Journal of Chemistry, vol. 37, nᵒ 5, p. 1312-1319.
Mots-clés : POLE 1, ROCS, SSO.
F. Chemla, F. Dulong, F. Ferreira, et A. Perez-Luna, « Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs », Beilstein Journal of Organic Chemistry, vol. 9, p. 236-245.
Résumé : The formation of alkylidenezinc carbenoids by 1,4- addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with beta-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at -30 degrees C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.
Mots-clés : alpha,alpha-disubstituted amino-acids, buttenberg-wiechell rearrangement, carbenoid formation, carbenoids, carbometallation, carbozincation, enantioselective reformatsky reaction, enolate derivatives, exchange-reactions, n-enoyloxazolidinones, nickel-catalyzed carbozincation, POLE 1, radicals, reactions involving organozinc, ROCS, SSO, tandem reaction, unactivated alkenes.
A. Denichoux, M. Cyklinsky, F. Chemla, F. Ferreira, et A. Pérez-Luna, « Conjugated Enyne Synthesis by Rearrangement of Acetylenic Epoxides Mediated by Low-Valence Organotitanium and Organozirconium Reagents », Synlett, vol. 24, nᵒ 08, p. 1001-1005.
A. Denichoux, L. Debien, M. Cyklinsky, M. Kaci, F. Chemla, F. Ferreira, et A. Perez-Luna, « Three-Carbon Homologation of Diorganozincs with Lithiated Acetylenic Epoxides », Journal of Organic Chemistry, vol. 78, nᵒ 1, p. 134-145.
Résumé : Reaction of dialkylzincs with lithiated acetylenic epoxides is described to give zincates that undergo a 1,2-metallate rearrangement by an anti-S(N)2' pathway. This rearrangement occurs with the transfer of an alkyl or a silyl group affording allenylzinc intermediates. Allenic and/or homopropargylic alcohols are obtained upon hydrolysis. Quenching the reaction mixture with aldehydes or ketones is shown to give access to 2-alkynyl-1,3-diols in a stereoselective manner.
Mots-clés : alpha-allenic alcohols, beta-hydroxy ketones, carbonyl-compounds, diastereoselective synthesis, homopropargylic alcohols, organic-synthesis, POLE 1, propargylic epoxides, ROCS, SSO, stereospecific synthesis, synthetic applications, zinc reagents.
M. M. Lorion, D. Gasperini, J. Oble, et G. Poli, « Palladium-Catalyzed Arylic/Allylic Aminations: Permutable Domino Sequences for the Synthesis of Dihydroquinolines from Morita-Baylis-Hillman Adducts », Organic Letters, vol. 15, nᵒ 12, p. 3050-3053.
Résumé : An efficient palladium-catalyzed synthesis of 1,2-dihydroquinolines has been developed via the reaction between anilines and Morita-Baylis-Hillman adducts derived from o-bromobenzaldehyde. This new Pd(0)-catalyzed pseudo-domino type I sequence Involves a Buchwald-Hartwig arylic amination and an allylic amination. When starting from an o-bromo allylic alcohol, the chronology Is arylic amination/allylic arylation. However, the sequence reverses when the reaction is performed on the corresponding o-bromo allylic acetate.
Mots-clés : acetates, Allylic alkylation, aromatic-amines, asymmetric-synthesis, cobalt nanoparticles, intramolecular heck reaction, one-pot synthesis, organic-synthesis, POLE 1, ring-closing metathesis, ROCS, sequential actions, SSO.

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