000061594 001__ 61594
000061594 005__ 20200221144249.0
000061594 0247_ $$2doi$$a10.1016/j.tetasy.2016.04.006
000061594 0248_ $$2sideral$$a94931
000061594 037__ $$aART-2016-94931
000061594 041__ $$aeng
000061594 100__ $$0(orcid)0000-0003-4196-5856$$aCarmona, Daniel
000061594 245__ $$aAsymmetric 1, 3-dipolar cycloaddition reactions between methacrylonitrile and nitrones catalysed by well-defined M(diphosphane) (M=Rh, Ir) complexes
000061594 260__ $$c2016
000061594 5060_ $$aAccess copy available to the general public$$fUnrestricted
000061594 5203_ $$aThe cationic half-sandwich aqua-complexes (¿ 5-C5Me5)M(PP*)(H2O)]SbF6]2 M=Rh, Ir; PP* =(R)-Benphos, (R)-Cyphos, (2R, 4R)-Norphos] catalyse the 1, 3-dipolar cycloaddition reaction of nitrones with methacrylonitrile with perfect regioselectivity, low-to-perfect endo-selectivity and low-to-moderate enantioselectivity. The active species involved in the catalytic process, (¿ 5-C5Me5)M(PP*)(methacrylonitrile)]SbF6]2, have been isolated and characterised as mixtures of the (S)- and (R)-at-metal epimers. NMR measurements of these mixtures indicated that the (R M)-isomers epimerise to the corresponding (S M) counterparts. The molecular structure of the rhodium complex (S Rh, R C)-(¿ 5-C5Me5)Rh((R)-Benphos)(methacrylonitrile)]SbF6]2 has been determined by X-ray diffraction methods. Diastereomerically pure (S Rh, R C)-(¿ 5-C5Me5)Rh(PP*)(methacrylonitrile)]SbF6]2 compounds catalyse stoichiometrically the above mentioned dipolar cycloaddition reaction with up to 90% enantiomeric excess, thus indicating the influence of the metal handedness on the catalytic stereochemical outcome. Catalysts can be recycled up to three times without a significant loss of either activity or selectivity.
000061594 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E63$$9info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2006-0015$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-32095$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-66079-P
000061594 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
000061594 590__ $$a2.126$$b2016
000061594 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b18 / 46 = 0.391$$c2016$$dQ2$$eT2
000061594 591__ $$aCHEMISTRY, ORGANIC$$b29 / 59 = 0.492$$c2016$$dQ2$$eT2
000061594 591__ $$aCHEMISTRY, PHYSICAL$$b80 / 145 = 0.552$$c2016$$dQ3$$eT2
000061594 592__ $$a0.754$$b2016
000061594 593__ $$aInorganic Chemistry$$c2016$$dQ2
000061594 593__ $$aPhysical and Theoretical Chemistry$$c2016$$dQ2
000061594 593__ $$aOrganic Chemistry$$c2016$$dQ2
000061594 593__ $$aCatalysis$$c2016$$dQ3
000061594 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000061594 700__ $$0(orcid)0000-0002-6160-3046$$aViguri, Fernando$$uUniversidad de Zaragoza
000061594 700__ $$aAsenjo, Ainara
000061594 700__ $$0(orcid)0000-0001-9071-563X$$aLamata, Pilar$$uUniversidad de Zaragoza
000061594 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando J.$$uUniversidad de Zaragoza
000061594 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar$$uUniversidad de Zaragoza
000061594 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000061594 773__ $$g27, 11-12 (2016), [26 pp.]$$pTetrahedron: asymmetry$$tTetrahedron: Asymmetry$$x0957-4166
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000061594 951__ $$a2020-02-21-13:26:54
000061594 980__ $$aARTICLE