Philipp Honegger1, Alexander Roller2, Michael Widhalm3. 1. Department of Computational Biological Chemistry, University of Vienna, Waehringer Strasse 17, A-1090 Vienna, Austria. 2. Department of Inorganic Chemistry, Faculty of Chemistry, University of Vienna, Waehringer Strasse 42, A-1090 Vienna, Austria. 3. Department of Chemical Catalysis, Faculty of Chemistry, University of Vienna, Waehringer Strasse 38, A-1090 Vienna, Austria.
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{(2Sp)-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[(2Sp)--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 {(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}[(2Sp)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C22H21O2PS)], [(2Sp)-2-ethenylferrocen-1-yl]{(2Sp)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C20H19OPS)], {(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}{(2Sp)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(R)-phosphine sulfide, [Fe2(C5H5)2(C22H23O3PS)], and {(2Sp)-2-[(1R)-1-benzylamino)ethyl]ferrocen-1-yl}[(2Sp)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C27H26NPS)]. All of the structures are accessible in one step from known precursors. open access.
In the couclass="Chemical">rse of aclass="Chemical">n oclass="Chemical">ngoiclass="Chemical">ng syclass="Chemical">nthetic pclass="Chemical">n class="Chemical">roject 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{(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocene}, [Fe2(C5H5)2(C24H25O4P)], and the otherphosphine sulfide is a purely planar-chiral compound (two planar chiral centres), i.e. bis[(2Sp)--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 fourrelated structures where the ferrocene units are not identical [(FcA)(FcB)(Ph)P]. These are {(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}[(2Sp)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C22H21O2PS)], [(2Sp)-2-ethenylferrocen-1-yl]{(2Sp)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C20H19OPS)], {(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}{(2Sp)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(R)-phosphine sulfide, [Fe2(C5H5)2(C22H23O3PS)], and {(2Sp)-2-[(1R)-1-benzylamino)ethyl]ferrocen-1-yl}[(2Sp)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C27H26NPS)]. All of the structures are accessible in one step from known precursors. open access.
Authors: Alexander M R Smith; Henry S Rzepa; Andrew J P White; Denis Billen; King Kuok Mimi Hii Journal: J Org Chem Date: 2010-05-07 Impact factor: 4.354