1,2-bis-(ditertbutylphosphinomethyl)benzene in catalysis

Phosphine;Ligands;Catalysis;Hydroformylation

Jiménez, Cristina ; Eastham, Graham ; Eastham, Graham

University:University of St Andrews

Department:Chemistry (School of)

关键词: Phosphine;    Ligands;    Catalysis;    Hydroformylation;   

Others  :  https://research-repository.st-andrews.ac.uk/bitstream/handle/10023/2650/CristinaJimenezPhDThesis.pdf?sequence=3&isAllowed=y

来源: DR-NTU

【 摘 要 】

Different diphosphine ligands having the structure shown below have beenstudied for carbonylation and hydroformylation reactions.Depending on the substituent on the phosphorus atoms the electronic and steric properties can be tuned to direct the reaction towards the desired products.Palladium methoxycarbonylation of a large variety of unsaturated compoundshas been attempted under very different conditions. The outcome of thesereactions was the achievement of the linear products with a selectivity higherthan 99.5 % under mild conditions of pressure and temperature.Chloroaromatic compounds have also been employed as substrates inmethoxycarbonylation reactions. Unexpected results were observed sincecarbonylation was possible only when a strong electron withdrawing group waspresent. The origin of the many side products from these reactions has beenelucidated.Rhodium hydroformylation was not as successful as palladiumMethoxycarbonylation since relatively severe conditions had to be used to getgood rates and good selectivity. In no case were there as good as those obtainedin the carbonylation reactions. However, unusual factors, such as the presence ofchlorine in the reaction media, have been found to influence either theconversion or the selectivity.