Аннотация:Diene rhodium complexes are important catalysts in modern organic synthesis. Herein, we report a new approach to the such complexes with the uncommon planar chirality. The synthesis is achieved by face-selective coordination of the prochiral 2,5-disubstituted-1,4-benzoquinones (R2-Q) with rhodium precursors containing the chiral auxiliary ligand S-salicyl-oxazoline (S-Salox). Such coordination leads to the formation of (R,R-R2-Q)Rh(S-Salox) complexes in high yields and with exceptional diastereoselectivity (d.r. > 20:1). Subsequent replacement of the auxiliary ligand provides various benzoquinone rhodium complexes with retention of the planar chirality. Combined theoretical and experimental studies show that due to their electron-withdrawing nature benzoquinones bind metals stronger than the related 1,4-cyclohexadiene, but weaker than other common diene ligands, such as cyclooctadiene.