Featuring Xantphos

This review highlights the use of a bisphosphine ligand group in homogeneous catalysis. This ligand group is known as the Xantphos-like ligands, which are based on the generic formula of 2,2'-bis(phosphino)diaryl ether. The synthesis of the main members is summarized and emphasis is given to ligands that can be easily synthesized, also on large scale. The catalytic applications are not comprehensively presented, but instead, about 20% of the examples from literature have been extracted, aiming at the demonstration of diversity, peculiar examples, historical development, design vs. trial and error, and new reactions. Metals ranging from group 7 to 11 have been used in a wide variety of reactions: hydroformylation, alkoxycarbonylation, hydrocyanation, cross-coupling reactions for many C-C and C-X bond forming reactions, carbonylative coupling reactions, phosphinations, etc.