TY - JOUR
T1 - Ligand effects in rhodium-catalyzed hydroformylation with bisphosphines
T2 - steric or electronic?
AU - Jiao, Yunzhe
AU - Torne, Marta Serrano
AU - Gracia, Jose
AU - Niemantsverdriet, J.W.
AU - van Leeuwen, Piet W.N.M.
PY - 2017/3/21
Y1 - 2017/3/21
N2 - Twelve commercially available bisphosphine ligands have been evaluated in rhodium-catalyzed hydroformylation reactions. All ligands exhibited high chemoselectivities for aldehyde formation. The highest enantioselectivity (53% ee) of styrene hydroformylation was achieved with (S)-BTFM-Garphos (L7) substituted with electron withdrawing substituents. High pressure NMR (HP-NMR) spectroscopy and in situ high pressure IR spectroscopy (HP-IR) were used to study the resting states of the catalyst species in the reactions. The ligand effect on the structures of the observable species was examined. Both electronic and steric factors were considered to contribute to the performance of the various ligands. The results showed that decreasing the phosphine basicity increased the enantioselectivity, while in the systems studied here the steric character plays a less important role than the electronic features in achieving good regioselectivities.
AB - Twelve commercially available bisphosphine ligands have been evaluated in rhodium-catalyzed hydroformylation reactions. All ligands exhibited high chemoselectivities for aldehyde formation. The highest enantioselectivity (53% ee) of styrene hydroformylation was achieved with (S)-BTFM-Garphos (L7) substituted with electron withdrawing substituents. High pressure NMR (HP-NMR) spectroscopy and in situ high pressure IR spectroscopy (HP-IR) were used to study the resting states of the catalyst species in the reactions. The ligand effect on the structures of the observable species was examined. Both electronic and steric factors were considered to contribute to the performance of the various ligands. The results showed that decreasing the phosphine basicity increased the enantioselectivity, while in the systems studied here the steric character plays a less important role than the electronic features in achieving good regioselectivities.
UR - http://www.scopus.com/inward/record.url?scp=85018411050&partnerID=8YFLogxK
U2 - 10.1039/c6cy01990k
DO - 10.1039/c6cy01990k
M3 - Article
AN - SCOPUS:85018411050
SN - 2044-4753
VL - 7
SP - 1404
EP - 1414
JO - Catalysis Science & Technology
JF - Catalysis Science & Technology
IS - 6
ER -