000112144 001__ 112144
000112144 005__ 20240319080947.0
000112144 0247_ $$2doi$$a10.1021/acs.joc.1c02699
000112144 0248_ $$2sideral$$a125698
000112144 037__ $$aART-2022-125698
000112144 041__ $$aeng
000112144 100__ $$aCapel, Estefanía
000112144 245__ $$aAbsence of intermediates in the BINOL-derived MG(II)/phosphate-catalyzed desymmetrizative ring expansion of 1-Vinylcyclobutanols
000112144 260__ $$c2022
000112144 5060_ $$aAccess copy available to the general public$$fUnrestricted
000112144 5203_ $$aThe catalyzed desymmetrizative ring expansion of alkenylcyclobutanols promoted by halofunctionalization of the alkene moiety with Nbromosuccinimide has been experimentally and computationally studied. The reaction yields highly enantioenriched cyclopentanones bearing two all-carbon quaternary stereocenters, one of them being generated in the rearrangement of the cyclobutane ring and the other by enantioselective desymmetrization. The reaction is competitive with the formation of a spiroepoxide, but it turns completely selective toward the cyclopentanone when a chiral bisphosphonium magnesium salt is employed as a catalyst. Mechanistic studies support the formation of an ion pair leading to a complex with only a unit of phosphoric acid, which is the resting state of the catalytic cycle. Calculations reproduce in an excellent way the observed reactivity and predict the effect exerted by the substituents of the aromatic ring linked to the double bond. The computational studies also revealed the reaction as a highly asynchronous concerted process taking place as one kinetic step but in two stages: (i) halogenation of the double bond and (ii) rearrangement of the cyclobutane. No intermediates are present in the reaction as energy minima. The experimental scope of the reaction further confirms the predictions for the observed reactivity and selectivity.
000112144 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E34-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2019-104090RB-100$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/PID2020-118422GB-I00$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-76155-R
000112144 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
000112144 590__ $$a3.6$$b2022
000112144 591__ $$aCHEMISTRY, ORGANIC$$b10 / 52 = 0.192$$c2022$$dQ1$$eT1
000112144 594__ $$a6.8$$b2022
000112144 592__ $$a0.892$$b2022
000112144 593__ $$aOrganic Chemistry$$c2022$$dQ1
000112144 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000112144 700__ $$aRodriguez-Rodriguez, Marta
000112144 700__ $$aUria, Uxue
000112144 700__ $$0(orcid)0000-0003-4249-6748$$aPedron, Manuel$$uUniversidad de Zaragoza
000112144 700__ $$0(orcid)0000-0003-3433-6701$$aTejero, Tomás$$uUniversidad de Zaragoza
000112144 700__ $$aVicario, José L
000112144 700__ $$0(orcid)0000-0002-2202-3460$$aMerino, Pedro$$uUniversidad de Zaragoza
000112144 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000112144 773__ $$g87, 1 (2022), 693-707$$pJ. org. chem.$$tJournal of Organic Chemistry$$x0022-3263
000112144 8564_ $$s7928524$$uhttps://zaguan.unizar.es/record/112144/files/texto_completo.pdf$$yVersión publicada
000112144 8564_ $$s2957170$$uhttps://zaguan.unizar.es/record/112144/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000112144 909CO $$ooai:zaguan.unizar.es:112144$$particulos$$pdriver
000112144 951__ $$a2024-03-18-12:39:33
000112144 980__ $$aARTICLE