000165090 001__ 165090
000165090 005__ 20251212165957.0
000165090 0247_ $$2doi$$a10.1021/om5003864
000165090 0248_ $$2sideral$$a86442
000165090 037__ $$aART-2014-86442
000165090 041__ $$aeng
000165090 100__ $$0(orcid)0000-0002-1430-1440$$aBatuecas, M.
000165090 245__ $$aRuthenium hydroxycarbenes as key intermediates in cycloisomerization and decarbonylative cyclization of terminal alkynals
000165090 260__ $$c2014
000165090 5203_ $$aThe complex [Ru(η5-C5H5)(CO)(κ1-OCMe2)(PiPr3)] BF4 (1) reacts with 3,3-bis(methoxycarbonyl)-5-hexyn-1-al to give the α,β-unsaturated cyclopentenylhydroxycarbene derivative [Ru(η5-C5H5){═C(OH)tiebar above startC═CHCH2C(CO2CH3)2tiebar above endCH2}(CO)(PiPr3)]BF4 (2), which undergoes deprotonation with Al2O3 to afford Ru(η5-C5H5){C(O)tiebar above startC═CHCH2C(CO2CH3)2tiebar above endCH2}(CO) (PiPr3) (3). In the presence of P2O5, the reaction of 1 with the alkynal leads to the alkenylvinylidene [Ru(η5-C5H5){═C═tiebar above startC—CH═CH—C(CO2CH3)2—tiebar above endCH2}(CO)(PiPr3)]BF4 (4), which yields the β,γ-unsaturated cyclopentenylhydroxycarbene [Ru(η5-C5H5){C(OH)tiebar above startCHCH═CHC(CO2CH3)2tiebar above endCH2}(CO)(PiPr3)]BF4 (5) by means of a 1,2-addition of water. Complex 5 slowly isomerizes into 2. The deprotonation of 5 with Al2O3 gives Ru(η5-C5H5){C(O)tiebar above startCHCH═CHC(CO2CH3)2tiebar above endCH2}(CO)(PiPr3) (6). Solvate Ru complex 1 and Ru hydroxycarbene 2 catalyze the cyclization of 3,3-bis(methoxycarbonyl)-5-hexyn-1-al to give mixtures of the cycloisomerized aldehyde 1,1-bis(methoxycarbonyl)-3-formylcyclopent-3-ene (7) and cycloalkene 1,1-bis(methoxycarbonyl)cyclopent-3-ene (8).
000165090 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E35$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-23459$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-28258$$9info:eu-repo/grantAgreement/ES/MINECO/JCI-2011-09946
000165090 540__ $$9info:eu-repo/semantics/closedAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000165090 590__ $$a4.126$$b2014
000165090 591__ $$aCHEMISTRY, ORGANIC$$b10 / 58 = 0.172$$c2014$$dQ1$$eT1
000165090 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 45 = 0.156$$c2014$$dQ1$$eT1
000165090 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000165090 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M. A.$$uUniversidad de Zaragoza
000165090 700__ $$0(orcid)0000-0002-5545-5112$$aGarcía-Yebra, C.$$uUniversidad de Zaragoza
000165090 700__ $$aGonzález-Rodríguez, C.
000165090 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000165090 700__ $$aSaá, C.
000165090 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000165090 773__ $$g33, 13 (2014), 3474-3480$$pOrganometallics$$tOrganometallics$$x0276-7333
000165090 8564_ $$s842222$$uhttps://zaguan.unizar.es/record/165090/files/texto_completo.pdf$$yVersión publicada
000165090 8564_ $$s3265563$$uhttps://zaguan.unizar.es/record/165090/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000165090 909CO $$ooai:zaguan.unizar.es:165090$$particulos$$pdriver
000165090 951__ $$a2025-12-12-14:42:28
000165090 980__ $$aARTICLE