烯烃的氢甲酰化反应是工业上最重要的均相催化反应之一,而通过烯烃的不对称氢甲酰化反应合成光学活性醛,对于药物、农药、香料和天然产物合成方面具有重要的意义.近年来,由于铑与膦配体形成的络合物在催化烯烃的不对称氢甲酰化反应中具有反应活性高、选择性好等优点而引起广泛关注.通过调控铑络合物中手性膦配体的电子与立体化学环境,已经成为实现不对称氢甲酰化反应高活性和高选择性最主要的方法.主要介绍了近期在铑催化的不对称氢甲酰化反应研究方面取得的进展,重点介绍几类代表性的手性膦配体在此类反应中的应用.
Hydroformylation is one of the most important processes of homogeneous catalysis in industry. Asymmetric hy- droformylation (AHF) of prochiral alkenes provides an efficient way to the synthesis of optically active aldehydes, which are versatile chiral intermediates for pharmaceuticals, agrochemicals, and other fine chemicals. So far, most of methods reported were focused on the use of Rh(I)-based catalysts, by virtue of their high catalytic activity and excellent chemoselectivity for the aldehydes. A key issue in searching for efficient asymmetric hydroformylation catalysts is the development of new chiral ligands. A number of chiral phosphorus ligands have been successfully developed for Rh(I)-catalyzed AHF reactions. In this review, the recent advances in the development of chiral ligands for the Rh-catalyzed asymmetric hydroformylaion of olefins have been surveyed.