Publication Type Journal Article
Title Hydrophosphonylation of aldehydes catalyzed by cyclopentadienyl ruthenium(II) complexes
Authors Ivania R. Cabrita Pedro R. Florindo Paulo J. Costa M. Conceição Oliveira A C Fernandes
Groups BioMol
Journal MOLECULAR CATALYSIS
Year 2018
Month May
Volume 450
Number
Pages 77-86
Abstract This work reports the first method for the synthesis of alpha-hydroxyphosphonates from aldehydes catalyzed by cyclopentadienyl ruthenium(II) complexes. The best results were obtained using the system HP(O)(OEt)(2)/[RuClCp(PPh3)(2)] (5 mol\%), affording the a-hydroxyphosphonates in good to excellent yields with high chemoselectivity. The catalyst [RuClCp(PPh3)(2)] can be used for at least 12 catalytic cycles with excellent activity and the reactions were carried out under solvent free conditions. DFT calculations were performed to rationalize the mechanism showing that the barriers associated with the H-phosphonate tautomer, HP(O)(OR)(2) are unrealistically high. This led us to propose that the catalyst promotes the tautomerization towards phosphite, P(OH)(OR)(2), via P-atom coordination, which accounts for the observed reactivity.
DOI http://dx.doi.org/10.1016/j.mcat.2018.03.001
ISBN
Publisher
Book Title
ISSN 2468-8231
EISSN
Conference Name
Bibtex ID ISI:000431158400009
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