Performances of symmetrical achiral ferrocenylphosphine ligands in palladium-catalyzed cross-coupling reactions: A review of syntheses, catalytic applications and structural properties

Ferrocene derivatives bearing donor atoms led to the generation of several classes of metallo-ligands, which collectively show an impressive diversity of applications, especially in metal-catalyzed modern organic reactions. Based on the impetus provided by the use of the diphosphine 1,1'-bis(diphenylphosphino)ferrocene (dppf) the investigations directed towards the synthesis of new ferrocenylphosphines remain of fundamental and industrial interest. The present review aims to describe the performances in palladium-catalyzed cross-coupling reactions of symmetrical achiral ferrocenylphosphine ligands, mainly diphosphines. We specifically choose to restrict our review efforts to these species due to their wide accessibility to all the chemist community. First, the synthetic routes that have been applied to the synthesis of these ferrocene derivatives are overviewed. Then, the recent advances in the chemistry of symmetric achiral di- and polyphosphine ferrocene-based ligands related to metalcatalyzed bond-forming reactions (C-C, C-N and C-O bonds) are discussed, with a special thrust to consolidate all the important work in this area. Finally, the structural properties of these ligands are discussed in relation with their reactivity, in the light of the mechanistic studies reported on parameters like coordination bite angle, electronic, steric and geometric features of ligands, conformation, and multidentarity. The many achievements and new challenges on this topic are summarized within the article. The literature cut-off date was beginning 2006. (C) 2007 Elsevier B.V. All rights reserved.