The Application Of Acylphosphines As Ligands Or Reagents In The Metal Rhodium (?) Catalyzed Reactions

Taking acylphosphine as electron-deficient phosphine ligand, utilizing the property of electron-withdrawing carbonyl group to adjust the electron density on the phosphorus atom, could promote the 1,2-addition reaction of rhodium catalyzed aldehydes. Acylphosphine compound act not only as ligand, but also as phosphine reagent which is applied in the C-P bond coupling reaction with rhodium catalyzed. The main contents are as follows:1, Development of electron-deficient acylphosphine ligands for rhodium catalyzed reactions.It is the first time that acylphosphine ligand is applied in the 1,2-addition reaction of metal rhodium catalyzed boronic acids to aldehydes, the reaction extends 24 substrates, including aromatic aldehydes, aliphatic aldehydes and cinnamic aldehyde, the highest yield up to 99%. In addition, with the chiral skeleton of (S)-BINOL synthesize chiral monodentate acylphosphine ligand. Furthermore, acylphosphine ligand is applied in other metal rhodium catalyzed addition reaction at the same time. This project provides a new method for chiral electron-deficient acylphosphine ligand, and introduces a new class of phosphine ligand to the metal catalyzed reaction.2, Development of the Rh-catalyzed C-P coupling reaction with acylphosphine and iodobenzene.In the rhodium-catalyzed C-P bond coupling reaction, acylphosphine reagents react with iodobenzenes to synthesize the triarylphosphine compounds. The C-P bond coupling reaction extends 30 substrates, including various iodobnezenes, benzoyl phosphine having different groups on the phenyl, with different groups on the two aryl of diphenylphosphine, the highest yield up to 98%.