0000000001320504

AUTHOR

Laurence Grimaud

showing 3 related works from this author

Multiple Roles of Isocyanides in Palladium-Catalyzed Imidoylative Couplings: A Mechanistic Study

2016

International audience; Kinetic, spectroscopic and computational studies examining a palladium-catalyzed imidoylative coupling highlight the dual role of isocyanides as both substrates and ligands for this class of transformations. The synthesis of secondary amides from aryl halides and water is presented as a case study. The kinetics of the oxidative addition of ArI with RNC-ligated Pd-0 species have been studied and the resulting imidoyl complex [(ArC=NR)Pd(CNR)(2)I] (Ar=4-F-C6H4, R = tBu) has been isolated and characterized by X-ray diffraction. The unprecedented ability of this RNC-ligated imidoyl-Pd complex to undergo reductive elimination at room temperature to give the amide in the p…

Denticityisocyanidepd-c bondStereochemistryeffective core potentialsIsocyanidechemistry.chemical_element010402 general chemistry01 natural sciencesMedicinal chemistry[ CHIM ] Chemical SciencesCatalysisReductive eliminationinsertionchemistry.chemical_compoundAmide[CHIM]Chemical Sciencescouplingsingle-carbonylation reactions010405 organic chemistryArylOrganic Chemistrycarbon-monoxidezerovalent palladiumGeneral Chemistrycyclopalladated complexespalladiumOxidative addition0104 chemical sciencesaryl halidesreaction mechanismsCatalytic cyclechemistryn-heterocyclessequential insertionPalladiumpalladated phenol derivatives
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From Benzofurans to Indoles: Palladium-Catalyzed Reductive Ring-Opening and Closure via β-Phenoxide Elimination

2018

International audience; Benzofurans can undergo ring-opening by a palladium-catalyzed process resulting in C−O bond breaking. Benzofuran-tethered 2-iodoanilines give synthetically interesting 2-(3-indolylmethyl)phenols in an overall reductive process. Mechanistic studies suggest that this unusual reaction proceeds by carbopalladation of benzofuran giving a 3-palladated 2,3-dihydrobenzofuran intermediate, which then fragments by an uncommon trans-elimination of the phenoxide group β to the metal. In this transformation, N,N-diisopropylethylamine (DIPEA) acts as a base and as a reducing agent: it regenerates palladium(0) from palladium(II), thus allowing catalytic turnover.

Indole test010405 organic chemistryChemistry[CHIM.ORGA]Chemical Sciences/Organic chemistryClosure (topology)chemistry.chemical_elementbenzofuranGeneral Chemistry[CHIM.CATA]Chemical Sciences/Catalysis010402 general chemistryRing (chemistry)palladium01 natural sciencesMedicinal chemistry0104 chemical sciencesCatalysischemistry.chemical_compoundHeck reactionindoleHeck reaction[CHIM]Chemical SciencesBenzofuranring openingComputingMilieux_MISCELLANEOUSPalladium
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CCDC 1485600: Experimental Crystal Structure Determination

2017

Related Article: Luca A. Perego, Paul Fleurat-Lessard, Laurent El Kaïm, Ilaria Ciofini, Laurence Grimaud|2016|Chem.-Eur.J.|22|15491|doi:10.1002/chem.201602913

Space GroupCrystallographyCrystal SystemCrystal StructureCell Parameterstrans-((t-butylimino)(4-fluorophenyl)methyl)-bis(t-butylisocyano)-iodo-palladium(ii)Experimental 3D Coordinates
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