000127872 001__ 127872
000127872 005__ 20231023120953.0
000127872 0247_ $$2doi$$a10.1002/chem.201502910
000127872 0248_ $$2sideral$$a93195
000127872 037__ $$aART-2015-93195
000127872 041__ $$aeng
000127872 100__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M. V.$$uUniversidad de Zaragoza
000127872 245__ $$aOxidation and ß-Alkylation of Alcohols Catalysed by Iridium(I) Complexes with Functionalised N-Heterocyclic Carbene Ligands
000127872 260__ $$c2015
000127872 5060_ $$aAccess copy available to the general public$$fUnrestricted
000127872 5203_ $$aThe borrowing hydrogen methodology allows for the use of alcohols as alkylating agents for C-C bond forming processes offering significant environmental benefits over traditional approaches. Iridium(I)-cyclooctadiene complexes having a NHC ligand with a O- or N-functionalised wingtip efficiently catalysed the oxidation and ß-alkylation of secondary alcohols with primary alcohols in the presence of a base. The cationic complex Ir(NCCH3)(cod)(MeIm(2- methoxybenzyl))]BF4] (cod=1, 5-cyclooctadiene, MeIm=1-methylimidazolyl) having a rigid O-functionalised wingtip, shows the best catalyst performance in the dehydrogenation of benzyl alcohol in acetone, with an initial turnover frequency (TOF0) of 1283 h-1, and also in the ß-alkylation of 2-propanol with butan-1-ol, which gives a conversion of 94 % in 10 h with a selectivity of 99 % for heptan-2-ol. We have investigated the full reaction mechanism including the dehydrogenation, the cross-aldol condensation and the hydrogenation step by DFT calculations. Interestingly, these studies revealed the participation of the iridium catalyst in the key step leading to the formation of the new C-C bond that involves the reaction of an O-bound enolate generated in the basic medium with the electrophilic aldehyde.
000127872 536__ $$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P
000127872 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000127872 590__ $$a5.771$$b2015
000127872 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b24 / 162 = 0.148$$c2015$$dQ1$$eT1
000127872 592__ $$a2.461$$b2015
000127872 593__ $$aChemistry (miscellaneous)$$c2015$$dQ1
000127872 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000127872 700__ $$aFernández-Tornos, J.
000127872 700__ $$0(orcid)0000-0002-9633-3285$$aModrego, F. J.$$uUniversidad de Zaragoza
000127872 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J. J.$$uUniversidad de Zaragoza
000127872 700__ $$0(orcid)0000-0001-7154-7239$$aOro, L. A.$$uUniversidad de Zaragoza
000127872 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000127872 773__ $$g21, 49 (2015), 17877-17889$$pChemistry (Weinh.)$$tChemistry - A European Journal$$x0947-6539
000127872 8564_ $$s610794$$uhttps://zaguan.unizar.es/record/127872/files/texto_completo.pdf$$yPostprint
000127872 8564_ $$s2735384$$uhttps://zaguan.unizar.es/record/127872/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000127872 909CO $$ooai:zaguan.unizar.es:127872$$particulos$$pdriver
000127872 951__ $$a2023-10-23-11:02:31
000127872 980__ $$aARTICLE