MoO2Cl2 as a Novel Catalyst for C-P Bond Formation and for Hydrophosphonylation of Aldehydes

resumo

This work reports the use of MoO2Cl2 as a novel catalyst for C-P bond formation, exemplified here by the hydrophosphonylation of aldehydes. A series of alpha-hydroxyphosphonates was prepared in excellent yields using the catalytic system HP(O)(OEt)(2)/MoO2Cl2 (5 mol %) under solvent-free conditions or at refluxing THF. DFT calculations indicate that the P=O bond coordinates to molybdenum while the P-H hydrogen is transferred to one Mo=O oxygen atom. The active species then reacts with the aldehyde to form the a-hydroxyphosphonates. The calculated activation barriers (free energies) are ca. 20 kcal mol(-1).

palavras-chave

ALPHA-HYDROXY PHOSPHONATES; MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; ENANTIOSELECTIVE HYDROPHOSPHONYLATION; POLARIZATION FUNCTIONS; SYSTEM SILANE/MOO2CL2; CARBONYL-COMPOUNDS; ORGANIC-MOLECULES; BASIS-SETS; REDUCTION

categoria

Chemistry

autores

de Noronha, RG; Costa, PJ; Romao, CC; Calhorda, MJ; Fernandes, AC

nossos autores

Grupos

agradecimentos

This research was supported by FCT, POCI, and FEDER through projects PTDC/QUI/71741/2006 and PTDCI/QUI/58925/2004. R.G.N. and PTC. thank FCT for postdoctoral grants (SFRH/ BPD/27215/2006 and (SFRH/BPD/27082/2006, respectively). The NMR spectrometers are part of the National NMR Network and were acquired with funds from FCT and FEDER.

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