Valorization of CO2: Preparation of 2-Oxazolidinones by Metal–Ligand Cooperative Catalysis with SCS Indenediide Pd Complexes

bibtex: ISI:000398986700049 bibtex\location:'1155 16TH ST, NW, WASHINGTON, DC 20036 USA',publisher:'AMER CHEMICAL SOC',type:'Article',affiliation:'Martin-Vaca, B; Bourissou, D (Reprint Author), Univ Toulouse, CNRS, UMR 5069, UPS,LHFA, 118 Route Narbonne, F-31062 Toulouse, France. Brunel, Paul; Monot, Julien; Martin-Vaca, Blanca; Bourissou, Didier, Univ Toulouse, CNRS, UMR 5069, UPS,LHFA, 118 Route Narbonne, F-31062 Toulouse, France. Kefalidis, Christos E.; Maron, Laurent, Univ Toulouse, CNRS, UMR 5215, INSA,UPS,LPCNO, 135 Ave Rangueil, F-31400 Toulouse, France.','author-email':'bmv@chimie.ups-tlse.fr dbouriss@chimie.ups-tlse.fr',da:'2018-12-05','doc-delivery-number':'ER7IS','funding-acknowledgement':'Centre National de la Recherche Scientifique; Universite de Toulouse; Agence Nationale de la Recherche [ANR CE6-CYCLOOP]; COST Action [CM1205 CARISMA]','funding-text':'This manuscript is in memory of Prof. Jose Barluenga. This work was supported financially by the Centre National de la Recherche Scientifique, the Universite de Toulouse, the Agence Nationale de la Recherche (ANR CE6-CYCLOOP), and the COST Action CM1205 CARISMA (Catalytic Routines for Small Molecule Activation). The authors are grateful to CalMip (CNRS, Toulouse, France) for calculation facilities. L.M. thanks the Institut Universitaire de France. Dr. J. Babinot is acknowledged for the preparation of substrates 1j,k.','journal-iso':'ACS Catal.','keywords-plus':'PALLADIUM PINCER COMPLEXES; CARBON-DIOXIDE INCORPORATION; N BOND FORMATION; CARBOXYLATIVE CYCLIZATION; EFFICIENT SYNTHESIS; PROPARGYLIC AMINES; ACETYLENIC AMINES; ATMOSPHERIC CO2; C-N; IONIC LIQUIDS','number-of-cited-references':'73',oa:'Bronze','orcid-numbers':'Kefalidis, Christos/0000-0002-1380-4337 Bourissou, Didier/0000-0002-0249-1769','research-areas':'Chemistry','researcherid-numbers':'Kefalidis, Christos/G-1067-2012','times-cited':'19','unique-id':'ISI:000398986700049','usage-count-last-180-days':'10','usage-count-since-2013':'32','web-of-science-categories':'Chemistry, Physical'\; International audience; The capture and utilization of CO, to prepare high value compounds is very attractive chemically and highly desirable socially. Indenediide-based Pd SCS pincer complexes are shown here to promote the carboxylative cyclization of propargylamines leading to 2-oxazolidinones under mild conditions (0.5-1 bar of CO2, DMSO, 40-80 degrees C, mol % Pd loading). The indenediide Pd complex is competitive with known catalysts. It proved successful for a wide range of propargylamines, including hitherto challenging substrates such as secondary propargylamines bearing tertiary alkyl groups at nitrogen, primary propargylamines, and propargylanilines. Thorough experimental (NMR) and computational (DFT) investigations were undertaken to gain mechanistic insights. Accordingly, (i) the resting state of the catalytic cycle is a Pd DMSO complex; (ii) the indenediide backbone and Pd center act in concert to activate the carbamic acid intermediate and promote its cyclization; (iii) proton shuttling is essential to lower the activation barriers of the initial amine carboxylation as well as of the proton transfers between the ligand backbone and the organic fragments at Pd.