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Título: | Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation | Autor: | Felgueiras, Alexandre P. Rodrigues, Fábio M. S. Carrilho, Rui M. B. Cruz, Pedro F. Rodrigues, Vítor H. Kégl, Tamás Kollár, László Pereira, Mariette M. |
Palavras-chave: | BINOL; menthol; X-ray diffraction; monophosphite synthesis; Mitsunobu reaction; DFT computational methods; Tolman’s cone angle; computed electronic parameter (CEP); rhodiumcatalysed hydroformylation | Data: | 19-Mar-2022 | Projeto: | UIDB/00313/2020 UIDP/00313/2020 PTDC/QUI-OUT/27996/2017 (DUALPI) CENTRO-07-CT62-FEDER-002012 (UC-NMR) NKFIH within the framework of the project TKP2021-EGA-17 |
Título da revista, periódico, livro ou evento: | Molecules | Volume: | 27 | Número: | 6 | Resumo: | Four stereoisomeric monoether derivatives, based on axially chiral (R)- or (S)-BINOL bearing a chiral (+)- or (-)-neomenthyloxy group were synthesised and fully characterised by NMR spectroscopy and X-ray crystallography. The respective tris-monophosphites were thereof prepared and fully characterised. The coordination ability of the new bulky phosphites with Rh(CO)2(acac), was attested by 31P NMR, which presented a doublet in the range of δ = 120 ppm, with a 1J(103Rh-31P) coupling constant of 290 Hz. The new tris-binaphthyl phosphite ligands were further characterised by DFT computational methods, which allowed us to calculate an electronic (CEP) parameter of 2083.2 cm-1 and an extremely large cone angle of 345°, decreasing to 265° upon coordination with a metal atom. Furthermore, the monophosphites were applied as ligands in rhodium-catalysed hydroformylation of styrene, leading to complete conversions in 4 h, 100% chemoselectivity for aldehydes and up to 98% iso-regioselectivity. The Rh(I)/phosphite catalytic system was also highly active and selective in the hydroformylation of disubstituted olefins, including (E)-prop-1-en-1-ylbenzene and prop-1-en-2-ylbenzene. | URI: | https://hdl.handle.net/10316/103391 | ISSN: | 1420-3049 | DOI: | 10.3390/molecules27061989 | Direitos: | openAccess |
Aparece nas coleções: | I&D CQC - Artigos em Revistas Internacionais |
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Stereoisomeric-TrisBINOLMenthol-Bulky-Monophosphites-Synthesis-Characterisation-and-Application-in-RhodiumCatalysed-HydroformylationMolecules.pdf | 2.5 MB | Adobe PDF | Ver/Abrir |
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