Ruthenium hydroxycarbenes as key intermediates in cycloisomerization and decarbonylative cyclization of terminal alkynals

Batuecas, M.; García-Yebra, C.; Oñate, E.; Saá, C.; Esteruelas, M. A.; González-Rodríguez, C.

doi:10.1021/om5003864

Ruthenium hydroxycarbenes as key intermediates in cycloisomerization and decarbonylative cyclization of terminal alkynals

Batuecas, M. ; Esteruelas, M. A. (Universidad de Zaragoza) ; García-Yebra, C. (Universidad de Zaragoza) ; González-Rodríguez, C. ; Oñate, E. ; Saá, C.

Resumen: The 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).
Idioma: Inglés
DOI: 10.1021/om5003864
Año: 2014
Publicado en: Organometallics 33, 13 (2014), 3474-3480
ISSN: 0276-7333
Factor impacto JCR: 4.126 (2014)
Categ. JCR: CHEMISTRY, ORGANIC rank: 10 / 58 = 0.172 (2014) - Q1 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 7 / 45 = 0.156 (2014) - Q1 - T1
Financiación: info:eu-repo/grantAgreement/ES/DGA/E35
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-23459
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-28258
Financiación: info:eu-repo/grantAgreement/ES/MINECO/JCI-2011-09946
Tipo y forma: Article (Published version)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
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Ruthenium hydroxycarbenes as key intermediates in cycloisomerization and decarbonylative cyclization of terminal alkynals