Rhodium/Phosphine catalysed selective hydroformylation of biorenewable olefins

Abstract

This work reports rhodium catalyzed selective hydroformylation of natural olefins like eugenol, estragole, anethole, prenol and isoprenol using biphenyl based Buchwald phosphine ligands (S‐Phos (L1), t‐Bu XPhos (L2), Ru‐Phos (L3), Johnphos (L4) and DavePhos (L5). Ru‐Phos (L3) ligand exhibited high impact on the hydroformylation of eugenol providing high selectivity (90%) of linear aldehyde as major product. In addition, internal natural olefins like anethole and prenol provided moderate to high selectivity (65% and 85% respectively) of branched aldehydes as a major products. The various reaction parameters such as influence of ligands, P/Rh ratio, syngas pressure, temperature, time and solvents have been studied. A high activity and selectivity gained on the way to the linear aldehydes it may be due to the bulky, steric cyclohexyl and isopropoxy groups present in L3 phosphine ligand. Moreover, this catalytic system was smoothly converting natural olefins into corresponding linear and branched aldehydes with higher selectivity under the mild reaction conditions.

Enhancing stability via confining Rh–P species in ZIF-8 for hydroformylation of 1-octene

“…1,2 Co-based and Rh-based catalysts are commonly used in industry. 3,4 Among them, Co-based catalysts exhibit low activity and need harsh reaction conditions. Comparatively, Rh-based catalysts with high activity and relatively mild reaction conditions have gradually become hotspots for research.…”

Rh Particles Supported on Sulfated g-C3N4: A Highly Efficient and Recyclable Heterogeneous Catalyst for Alkene Hydroformylation

“…Today, this transformation represents one of the most large-scale reactions in industry. More than ten million tons of "oxo chemicals" are manufactured by the hydroformylation reaction [7,8].…”

Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a RhPPh3 catalyst

“…As well known, the hydroxymethylation is an important reaction for introduction of a hydroxymethyl group into a molecular. [15][16][17][18][19][20][21][22] It has been reported that BAs could be synthesized via hydroxymethylation of aryl halides and triflates [23] ; however, the catalyst was rather complicated and high loadings (the combination of 5 mol % Pd (dba) 2 , 12 mol% Ru-phos, and 1.5 equiv. Na 2 CO 3 ), and the reactants were expensive resulting in a high-cost route.…”