Hydroformylation—Homogeneous

Abstract

The hydroformylation or oxo‐synthesis is one of the most important transition metal assisted homogeneous catalytic transformation, providing industrial‐scale production of aldehydes and alcohols. The hydroformylation—homogeneous article presents the basic chemistry and kinetics of hydroformylation, solvents of hydroformlylation, and side reactions accompanying hydroformylation. The detailed reaction mechanisms related to the cobalt‐ and rhodium‐modified and unmodified catalysts are presented as well. The chemistry of the individual steps of the classic catalytic cycle based on results of model reactions and spectroscopic investigations is discussed and is followed by an overview of different catalyst modifiers such as phosphine and phosphite ligands.

Recent Advances in Catalytic Carbonylation Reactions in Alternative Reaction Media

“…The first carbonylation reaction, which led to the formation of aldehydes by the reaction of a carbon‐carbon double bond with carbon monoxide and dihydrogen in the presence of a transition metal catalyst, was discovered by German chemist Otto Roelen in 1938. [ 17‐18 ] The accidental discovery of CO addition to olefinic bond of ethylene [ 19 ] was made during the development of the cobalt‐catalyzed Fischer‐Tropsch reaction, while the formation of propanal was observed from ethylene and syngas (H 2 : CO = 1 : 1). The product yield became less and less by increasing the temperature indicating the presence of a temperature‐sensitive species [HCo(CO) 4 ].…”

“…The product yield became less and less by increasing the temperature indicating the presence of a temperature‐sensitive species [HCo(CO) 4 ]. [ 19 ] At the same time and in Germany as well, Walter Reppe revealed that methanol could be carbonylated in the presence of metal carbonyls of VIIIB elements as catalysts. [ 20 ] However, the reaction requires extremely high pressure (up to 700 bar) and temperature ( ca .…”

Hydroformylation of Alkenes over Phosphorous-Free Rhodium Supported on N-Doped Silica

“…Hydroformylation (oxo process), discovered by Otto Roelen as far back as 1938, is still widely used to produce aldehydes, which can further be converted into alcohols, ethers and esters, carboxylic acids, aliphatic amines, and other derivatives with high added value [1]. The modern industrial hydroformylation process is based on homogeneous rhodium systems [2][3][4][5]. However, one of the main problems of homogeneous hydroformylation has long been the difficulty of the recovery of the catalyst from the reaction mixture and the purification of the catalyst.…”