Synthesis and characterization of enantiopure planar-chiral phosphorus-linked diferrocenes

Abstract

In the course of an ongoing synthetic project on cyclic diferrocenylphosphines, we obtained a group of planar-chiral diferrocenyl compounds useful as precursors for subsequent cyclization. Here we report the crystal structures of two symmetric compounds [(FcA)2(Ph)P], one of which contains four stereogenic centres (two C chiral and two planar chiral centres), i.e. 1,1′-(phenylphosphanediyl)bis{(2S p)-2-[(1R)-1-(acetyloxy)ethyl]ferrocene}, [Fe2(C5H5)2(C24H25O4P)], and the other phosphine sulfide is a purely planar-chiral compound (two planar chiral centres), i.e. bis[(2S p) - 2-ethenylferrocen-1-yl]phenylphosphane sulfide, [Fe2(C5H5)2(C20H17PS)]. Owing to the stereocentres present, reactions performed on [(FcA)2(Ph)P]-type compounds strongly favour one ferrocene unit over the other due to diastereoselectivity. Furthermore, we present four related structures where the ferrocene units are not identical [(FcA)(FcB)(Ph)P]. These are {(2S p)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}[(2S p)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C22H21O2PS)], [(2S p)-2-ethenylferrocen-1-yl]{(2S p)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C20H19OPS)], {(2S p)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}{(2S p)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(R)-phosphine sulfide, [Fe2(C5H5)2(C22H23O3PS)], and {(2S p)-2-[(1R)-1-benzylamino)ethyl]ferrocen-1-yl}[(2S p)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C27H26NPS)]. All of the structures are accessible in one step from known precursors.