Institut de Chimie Moléculaire et des Matériaux d'Orsay

Polycyclisations Catalytiques

Over the past 5 years, our group has remained focused on the development of original homogeneous catalytic methods towards the synthesis of cyclic compounds.One aspect of our work aims at circumventing the limitations of late transition metal catalysis by devising new activation protocols that allow to control the decomposition of the complex and therefore significantly diminish its loading. The second aspect is to replace noble metals by more abundant elements from the first row transition metal series, or by main group metals. All these projects have been supported by computational studies to rationalize the reaction mechanisms. Computational chemistry, especially DFT calculations, still occupies a prominent position in the group and constitutes on its own the third aspect of our investigations.

We have exploited the exceptional σ-Lewis acidity of Ca(II) complex, sometimes exacerbated by the use of hexafluoroisopropanol as solvent (HFIP), to activate electron-poor C=C bonds in hydroamination reactions, or to activate Csp3-O bonds for the synthesis of carbocycles or oxygen- or nitrogen-containing heterocycles. In particular, the low-tech air-stable calcium pre-catalyst Ca(NTf2)showed an exceptional versatility in reactions leading to furans, pyrroles or pyrrolidines.

 

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The borrowing hydrogen strategy has been applied to the ethylation of imines, using an air-stable iron complex as precatalyst. This approach has opened new perspectives in this area, as it allowed the synthesis of unsymmetric tertiary amines from readily available substrates and ethanol as C2-building block. A variety of imines bearing electron-rich aromatic or alkyl groups at the nitrogen atom could be efficiently reductively alkylated, without requiring the use of molecular hydrogen.

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We have developed new families of cationic Ga(I), Ga(III), In(I) and In(III) catalysts able to imitate the behavior of noble transition metal complexes in π-acid catalysis or transfer hydrogenation. These species exhibit either NHC or fluorobenzene ligands. They behave as soft Lewis acids able to trigger the formation of highly delocalized non-classical carbocations from alkynes and alkenes. They are especially useful in skeletal reorganization reactions leading to polycyclic compounds after C-C or C-H bond formation.

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In order to improve the overall efficiency of gold-catalyzed transformations, we have discovered that Cu(I) and Cu(II) salts could activate LAuCl precatalysts, while lowering their decay into inactive nanoparticles. This decomposition phenomenon is typically observed with Ag(I) activators, which are commonly used to generate the active cationic gold complex. On the other hand, the Au/Cu catalytic system proved versatile and allowed to carry out a variety of reactions with very low loadings of the gold precatalyst and without requiring tedious ligand design. Indeed, simple phosphines could be used successfully on gram-scale reactions.

 

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In addition to providing a mechanistic insight into the aforementioned and other in-house projects, DFT computations have been carried out on various collaborative projects on Au-, Rh-, Fe-, Pd-catalyzed reactions and other catalytic processes leading to polycyclic compounds. Among recent achievements, we have deciphered the intriguing Pd-catalyzed carbocyclization leading to polycyclic cyclooctatetraenes in collaboration with J. Suffert and G. Blond from Unistra.

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Recent publications:

Synthesis of Cyclopenta[b]piperazinones via an Azaoxyallyl Cation. B. Baldé, G. Force, L. Marin, R. Guillot, E. Schulz, V. Gandon, D. Lebœuf, Org. Lett., 2018, 20, 7405-7409

Gallium-Catalyzed Scriabine Reaction. M. Pareek, C. Bour, V. Gandon, Org. Lett., 2018, 20, 6957-6960

Calcium(II)-Catalyzed Intermolecular Hydroarylation of Deactivated Styrenes in Hexafluoroisopropanol. C. Qi, V. Gandon, D. Lebœuf, Angewandte Chemie International Edition, 2018, 57, 14245-14249

Palladium(II)-Catalyzed Diastereoselective 2,3-Trans C(sp3)-H Arylation of Glycosides. N. Probst, G. Grelier, S. Dahaoui, M. Alami, V. Gandon, S. Messaoudi, ACS Catalysis, 2018, 8, 7781-7786

Spatially encoded diffusion-ordered NMR spectroscopy of reaction mixtures in organic solvents. G. Hamdoun, L. Guduff, C. Van Heijenoort, C. Bour, V. Gandon, J.-N. Dumez, Analyst, 2018, 143, 3458-3464

Synthesis of 3-Substituted 3-Bromo-1-phenylallenes from Alkynylcycloheptatrienes. M. Vayer, R. Guillot, C. Bour, V. Gandon, J. Org. Chem., 2018, 83, 11309–11317

Calcium(II)-Catalyzed Intra- and Intermolecular Hydroamidation of Unactivated Alkenes in Hexafluoroisopropanol Alcohol. C. Qi, F. Hasenmaile, V. Gandon, D. Lebœuf, ACS Catalysis, 2018, 8, 1734-1739

Intermolecular rhodium(II)-catalyzed allylic C(sp3)-H amination of cyclic enamides. R. Rey-Rodriguez, G. Jestin, V. Gandon, G. Grelier, P. Retailleau, B. Darses, P. Dauban, I. Gillaizeau, Advanced Synthesis & Catalysis, 2018, 360, 513-518

Reactions Involving Tryptamines and δ-Allenyl Aldehydes: Competition between Pictet-Spengler Reaction and Cyclization to 1-Aminotetralins. V. Gobe, V. Gandon, X. Guinchard, Advanced Synthesis & Catalysis, 2018, 360, 1280-1288

Iron-Catalyzed Reductive Ethylation of Imines with Ethanol. M. Vayer, S. P. Morcillo, J. Dupont, V. Gandon, C. Bour, Angewandte Chemie, International Edition, 2018, 57, 3228-3232

Dissecting the Gold(I)-Catalyzed Carboaminations of N-Allyl Tetrahydro-β-carbolines to Allenes. V. Gobe, M. Dousset, P. Retailleau, V. Gandon, X. Guinchard, Journal of Organic Chemistry, 2018, 83, 898-912

A diversity-oriented synthesis of cyclopenta[b]pyrroles and related compounds through a calcium(ii)/copper(ii) catalytic sequence. L. Marin, R. Guillot, V. Gandon, E. Schulz, D. Lebœuf, Org. Chem. Front., 2018, 5, 640-647

Catalytic Use of Low-Valent Cationic Gallium(I) Complexes as π-Acids. Z. Li, G. Thiery, M. R. Lichtenthaler, R. Guillot, I. Krossing, V. Gandon, C. Bour, Advanced Synthesis & Catalysis, 2018, Volume360, Issue3, 544-549

Triflic acid as an efficient Brønsted acid promoter for the Umpolung of N-Ac indoles in hydroarylation reactions. R. K. Nandi, A. Perez-Luna, D. Gori, R. Beaud, R. Guillot, C. Kouklovsky, V. Gandon, G. Vincent, Adv. Synth. Catal., 2018, 360, 161–172

Functionalization of Mo132 Keplerate Nanocapsules by Cyclic Carboxylates: L-proline vs Cyclopentanecarboxylate. M. Awada, S. Floquet, M. Haouas, N. Watfa, J. Marrot, C. Roch-Marchal, V. Coeffard, C. Greck, C. Bour, V. Gandon, F. Taulelle, E. Cadot, Current Inorganic Chemistry, 2017, 7, 39-47

Intramolecular Inverse Electron-Demand [4 + 2] Cycloadditions of Ynamides with Pyrimidines: Scope and Density Functional Theory Insights. G. Duret, R. Quinlan, B. Yin, R. E. Martin, P. Bisseret, M. Neuburger, V. Gandon, N. Blanchard, Journal of Organic Chemistry, 2017, 82, 1726-1742

Carbon-Carbon and Carbon-Heteroatom Bond-Forming Transformations Catalyzed by Calcium(II) Triflimide. D. Lebœuf, V. Gandon, Synthesis, 2017, 49, 1500-1508

Substitution of the Participating Group of Glycosyl Donors by a Halogen Atom: Influence on the Rearrangement of Transient Orthoesters Formed during Glycosylation Reactions. A. Joosten, M. Boultadakis-Arapinis, V. Gandon, L. Micouin, T. Lecourt, Journal of Organic Chemistry, 2017, 82, 3291-3297

Calcium(II)-Catalyzed Alkenylation of N-Acyliminiums and Related Ions with Vinylboronic Acids. C. Qi, V. Gandon, D. Lebœuf, Advanced Synthesis & Catalysis, 2017, 359, 2671-2675

Enantioselective gold(I)-catalyzed rearrangement of cyclopropyl-substituted 1,6-enynes into 2-oxocyclobutyl-cyclopentanes. Z. Wu, D. Lebœuf, P. Retailleau, V. Gandon, A. Marinetti, A. Voituriez, Chemical Communications (Cambridge, United Kingdom), 2017, 53, 7026-7029

Intramolecular Pd-Catalyzed Anomeric C(sp3)-H Activation of Glycosyl Carboxamides. N. Probst, G. Grelier, N. Ghermani, V. Gandon, M. Alami, S. Messaoudi, Organic Letters, 2017, 19, 5038-5041

Synthesis of Spiroindolenines via Regioselective Gold(I)-Catalyzed Cyclizations of N-Propargyl Tryptamines. V. Magne, A. Marinetti, V. Gandon, A. Voituriez, X. Guinchard, Advanced Synthesis & Catalysis, 2017, 359, 4036-4042

Asymmetric FeII-Catalyzed Thia-Michael Addition Reaction to α,β-Unsaturated Oxazolidin-2-one Derivatives. S. Lauzon, H. Keipour, V. Gandon, T. Ollevier, Organic Letters, 2017, 19, 6324-6327

One-Pot Assembly of Highly Functionalized Cyclopenta[b]pyrroles via a Calcium(II)- and Copper(II)-Catalyzed Reaction Sequence. L. Marin, V. Gandon, E. Schulz, D. Lebœuf, Advanced Synthesis & Catalysis, 2017, 359, 1157-1163

Revealing the Activity of pi-Acid Catalysts Using a 7-Alkynyl Cycloheptatriene. V. Gandon, M. Vayer, R. Guillot, C. Bour, Chemistry – A European Journal, 2017, Volume 23, Issue 56, 13901–13905

Revealing the Electrophilicity of N-Ac Indoles with FeCl3: a mechanistic study. R. Beaud, R. K. Nandi, A. Perez-Luna, R. Guillot, D. Gori, C. Kouklovsky, N. E. Ghermani, V. Gandon, G. Vincent, Chem. Commun., 2017, 53, 5834 - 5837

Catalytic Activity of Gold(I) Complexes with Hemilabile P,N Ligands. B. Michelet, D. Lebœuf, C. Bour, K. Škoch, F. Horký, P. Štěpnička, V. Gandon, ChemPlusChem, 2017, 82, 442-448

Synthesis and Characterizations of Keplerate Nanocapsules Incorporating L- and D-Tartrate Ligands. M. Awada, S. Floquet, J. Marrot, M. Haouas, S. P. Morcillo, C. Bour, V. Gandon, V. Coeffard, C. Greck, E. Cadot, Journal of Cluster Science, 2017, 1-14

Synthesis, biological evaluation and molecular modeling studies on novel quinonoid inhibitors of CDC25 phosphatases. E. Evain-Bana, L. Schiavo, C. Bour, D. A. Lanfranchi, S. Berardozzi, F. Ghirga, D. Bagrel, B. Botta, G. Hanquet, M. Mori, Journal of Enzyme Inhibition and Medicinal Chemistry, 2017, 32, 113

Acid-catalysed intramolecular addition of [small beta]-ketoesters to 1,3-dienes. M. Vayer, W. Fang, R. Guillot, S. Bezzenine-Lafollee, C. Bour, V. Gandon, Org. Biomol. Chem., 2017, 15, 584-588

Calcium‐Catalyzed Synthesis of Polysubstituted 2‐Alkenylfurans from β‐Keto Esters Tethered to Propargyl Alcohols. S. P. Morcillo, D. Lebœuf, C. Bour, V. Gandon, Chemistry – A European Journal, 2016, 22, 16974-16978

Stapled helical o-OPE foldamers as new circularly polarized luminescence emitters based on carbophilic interactions with Ag(i)-sensitivity. S. P. Morcillo, D. Miguel, L. Alvarez De Cienfuegos, J. Justicia, S. Abbate, E. Castiglioni, C. Bour, M. Ribagorda, D. J. Cardenas, J. M. Paredes, L. Crovetto, D. Choquesillo-Lazarte, A. J. Mota, M. C. Carreno, G. Longhi, J. M. Cuerva, Chem. Sci., 2016, 7, 5663-5670

Gold(I)-Catalyzed Carboaminations of Allenes by N-Allyltetrahydro-β-carbolines: An Experimental and Theoretical Study. V. Gobe, M. Dousset, P. Retailleau, V. Gandon, X. Guinchard, Advanced Synthesis & Catalysis, 2016, 358, 3960-3965

Diastereoselective synthesis of 2,5-disubstituted-3-hydroxy-tetrahydrofurans through a counterion-directed Tsuji-Trost reaction. X. Caumes, L. Jeanne-Julien, C. Khelifi, V. Gandon, E. Roulland, Org. Chem. Front., 2016, 3, 1462-1466

Harnessing the Lewis Acidity of HFIP through its Cooperation with a Calcium(II) Salt: Application to the Aza-Piancatelli Reaction. D. Lebœuf, L. Marin, B. Michelet, A. Perez-Luna, R. Guillot, E. Schulz, V. Gandon, Chemistry – A European Journal, 2016, 22, 16165-16171

Catalytic applications of [IPr[middle dot]GaX2][SbF6] and related species. B. Michelet, S. Tang, G. Thiery, J. Monot, H. Li, R. Guillot, C. Bour, V. Gandon, Org. Chem. Front., 2016, 3, 1603-1613

Inverse Electron-Demand [4 + 2]-Cycloadditions of Ynamides: Access to Novel Pyridine Scaffolds. G. Duret, R. Quinlan, R. E. Martin, P. Bisseret, M. Neuburger, V. Gandon, N. Blanchard, Organic Letters, 2016, 18, 1610-1613

Synthesis of Cyclooctatetraenes through a Palladium-Catalyzed Cascade Reaction. S. Blouin, V. Gandon, G. Blond, J. Suffert, Angewandte Chemie, International Edition, 2016, 55, 7208-7211

Chiral Phosphate in Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition: Ligand, Counterion, or Both?. M. Barbazanges, E. Caytan, D. Lesage, C. Aubert, L. Fensterbank, V. Gandon, C. Ollivier, Chemistry - A European Journal, 2016, 22, 8553-8558

Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes. J. Ciesielski, G. Dequirez, P. Retailleau, V. Gandon, P. Dauban, Chemistry - A European Journal, 2016, 22, 9338-9347

Assessing ligand and counterion effects in the noble metal catalyzed cycloisomerization reactions of 1,6-allenynes: a combined experimental and theoretical approach. F. Jaroschik, A. Simonneau, G. Lemiere, K. Cariou, N. Agenet, H. Amouri, C. Aubert, J.-P. Goddard, D. Lesage, M. Malacria, Y. Gimbert, V. Gandon, L. Fensterbank, ACS Catalysis, 2016, 6, 5146-5160

Site-Selective Calcium-Catalyzed/Organocatalyzed Condensation of Propargyl Alcohols Tethered to β-Keto Esters. S. P. Morcillo, M. Presset, S. Floquet, V. Coeffard, C. Greck, C. Bour, V. Gandon, European Journal of Organic Chemistry, 2016, 2016, 2688-2694

Use of Planar Chiral Ferrocenyl­phosphine-Gold(I) Complexes in the Asymmetric Cycloisomerization of 3-Hydroxylated 1,5-Enynes. Z. Wu, P. Retailleau, V. Gandon, A. Voituriez, A. Marinetti, European Journal of Organic Chemistry, 2016, 2016, 70-75

Copper (II) triflate as additive in low loading Au(I)-catalyzed hydroalkylation of unactivated alkenes. W. Fang, M. Presset, A. Guérinot, C. Bour, S. Bezzenine-Lafollée, V. Gandon, Organic Syntheses, 2015, 92, 117-130

Chiral Calcium-BINOL Phosphate Catalyzed Diastereo- and Enantioselective Synthesis of syn-1,2-Disubstituted 1,2-Diamines: Scope and Mechanistic Studies. C. Lalli, A. Dumoulin, C. Lebee, F. Drouet, V. Guerineau, D. Touboul, V. Gandon, J. Zhu, G. Masson, Chemistry - A European Journal, 2015, 21, 1704-1712

A Terminal, Fluxional η4-Benzene Complex with a Thermally Accessible Triplet State is the Primary Photoproduct in the Intercyclobutadiene Haptotropism of (CpCo)phenylenes. T. A. Albright, R. Drissi, V. Gandon, S. Oldenhof, O. A. Oloba-Whenu, R. Padilla, H. Shen, K. P. C. Vollhardt, V. Vreeken, Chemistry - A European Journal, 2015, 21, 4546-4550

Cycloisomerization of Conjugated Trienones and Isomeric 2H-Pyrans: Unified Strategy toward Cyclopenta[b]furans. M. J. Riveira, G. N. Quiroga, E. G. Mata, V. Gandon, M. P. Mischne, Journal of Organic Chemistry, 2015, 80, 6515-6519

Double-Stereodifferentiation in Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition: Chiral Ligand/Chiral Counterion Matched Pair. M. Auge, A. Feraldi-Xypolia, M. Barbazanges, C. Aubert, L. Fensterbank, V. Gandon, E. Kolodziej, C. Ollivier, Organic Letters, 2015, 17, 3754-3757

Hypervalent-Iodine-Mediated Synthesis of 1,2-Dispirodienones: Experimental and Theoretical Investigations. T. Hromjakova, P. Retailleau, L. Grimaud, V. Gandon, L. Chabaud, C. Guillou, European Journal of Organic Chemistry, 2015, 2015, 7494-7503

CaII-Catalyzed Alkenylation of Alcohols with Vinylboronic Acids. D. Lebœuf, M. Presset, B. Michelet, C. Bour, S. Bezzenine-Lafollée, V. Gandon, Chemistry – A European Journal, 2015, 21, 11001-11005

Non-Innocent Behavior of Substrate Backbone Esters in Metal-Catalyzed Carbocyclizations and Friedel–Crafts Reactions of Enynes and Arenynes. B. Michelet, G. Thiery, C. Bour, V. Gandon, J. Org. Chem., 2015, 80, 10925-10938

New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids. C. Bour, V. Gandon, Synlett, 2015, 26, 1427-1436

Gallium(III)- and calcium(II)-catalyzed Meyer-Schuster rearrangements followed by intramolecular aldol condensation or endo-Michael addition. M. Presset, B. Michelet, R. Guillot, C. Bour, S. Bezzenine-Lafollee, V. Gandon, Chem. Commun., 2015, 51, 5318-5321

First Evidence for the Existence of Hexafluoroantimonic(V) Acid. C. Bour, R. Guillot, V. Gandon, CHEMISTRY-A EUROPEAN JOURNAL, 2015, Volume: 21 Issue: 16, 6066-6069

Dibromoindium(III) cations as a pi-Lewis acid: characterization of [IPr center dot InBr2][SbF6] and its catalytic activity towards alkynes and alkenes. B. Michelet, J.-R. Colard-Itte, G. Thiery, R. Guillot, C. Bour, V. Gandon, CHEMICAL COMMUNICATIONS, 2015, Volume: 51 Issue: 34, 7401-7404