Please use this identifier to cite or link to this item: https://hdl.handle.net/10316/103391
Title: Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation
Authors: Felgueiras, Alexandre P. 
Rodrigues, Fábio M. S. 
Carrilho, Rui M. B. 
Cruz, Pedro F. 
Rodrigues, Vítor H. 
Kégl, Tamás
Kollár, László 
Pereira, Mariette M. 
Keywords: BINOL; menthol; X-ray diffraction; monophosphite synthesis; Mitsunobu reaction; DFT computational methods; Tolman’s cone angle; computed electronic parameter (CEP); rhodiumcatalysed hydroformylation
Issue Date: 19-Mar-2022
Project: 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 
Serial title, monograph or event: Molecules
Volume: 27
Issue: 6
Abstract: 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
Rights: openAccess
Appears in Collections:I&D CQC - Artigos em Revistas Internacionais

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