000084670 001__ 84670
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000084670 0247_ $$2doi$$a10.1002/chem.201601301
000084670 0248_ $$2sideral$$a98884
000084670 037__ $$aART-2016-98884
000084670 041__ $$aeng
000084670 100__ $$0(orcid)0000-0002-0116-9743$$aMéndez, Isabel
000084670 245__ $$aTemperature Dual Enantioselective Control in a Rhodium-Catalyzed Michael-Type Friedel-Crafts Reaction: A Mechanistic Explanation
000084670 260__ $$c2016
000084670 5060_ $$aAccess copy available to the general public$$fUnrestricted
000084670 5203_ $$aBy changing the temperature from 283 to 233 K, the S (99% ee)orR (96 % ee)enantiomer of the Friedel–Crafts (FC) adduct of the reaction between N-methyl-2-methylindole and trans-b-nitrostyrene can be obtained by using (S Rh ,R C )-[(h 5 -C 5 Me 5 )Rh{(R)-Prophos}(H 2 O)][SbF 6 ] 2 as the catalyst precursor.This catalytic systempresents two otheruncom - mon features:1)The ee changes with reactio ntime showing trends that depend on the reactiontemperature and 2) an increase in the catalyst loading results in adecrease in the ee of the S enantiom er.Detection and characteriza tion of the intermediate metal-nitroalkene and metal–aci-nitro complexes, the free aci-nitro compound, and the FC adduct-complex, together with solution NMR measuremen ts, theo- retical calculations, and kinetic stu dies have allowed us to propose two plausible alternative catalytic cycles. On the basis of these cycles,all the above -mentioned observations can be rationalized. In particular,the reversibility of one of the cycles toget her with the kinetic resolution of the intermediate aci-nitro complexes accountfor the high ee values achieved in both antipodes.Onthe other hand, the results of kinetic measurements explain the unusual effect of the increment in catalyst loading.
000084670 536__ $$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
000084670 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000084670 590__ $$a5.317$$b2016
000084670 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b29 / 166 = 0.175$$c2016$$dQ1$$eT1
000084670 592__ $$a2.351$$b2016
000084670 593__ $$aChemistry (miscellaneous)$$c2016$$dQ1
000084670 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000084670 700__ $$0(orcid)0000-0002-8845-0174$$aRodríguez-Martínez, Ricardo$$uUniversidad de Zaragoza
000084670 700__ $$0(orcid)0000-0001-5823-7965$$aPolo, Víctor$$uUniversidad de Zaragoza
000084670 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vicenzo
000084670 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando J.$$uUniversidad de Zaragoza
000084670 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar$$uUniversidad de Zaragoza
000084670 700__ $$0(orcid)0000-0003-4196-5856$$aCarmona, Daniel
000084670 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000084670 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000084670 773__ $$g22, 31 (2016), 11064-11083$$pChemistry (Weinh.)$$tChemistry - A European Journal$$x0947-6539
000084670 8564_ $$s1833385$$uhttps://zaguan.unizar.es/record/84670/files/texto_completo.pdf$$yPostprint
000084670 8564_ $$s116428$$uhttps://zaguan.unizar.es/record/84670/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
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000084670 951__ $$a2020-02-21-13:19:31
000084670 980__ $$aARTICLE