The Synthesis Of Chiral Ferrocene Imine Ring Metal Compounds, Separation And Identification

Abstract In this thesis, the syntheses of chiral ferrocenylimines and their cyclomercuration, cyclopaliadation were studied in the following three aspects: 1. Ferrocenylimines (+)-(R)-2 and (-)-(S)-2 were prepared by the condensation of benzoylferrocene with R-(+)-cL-phenyl-ethylamine [(+}-(R)-l] and S-(-)-phenyl-ethylamine((-)-(S)-l], respectively, in the presence of freshly activated A1203. The products (+)-(R)-2 and (-)-{S)-2 were characterized by elemental analyses, IR and 慔 NMR spectra. Ph (+)-(R)-1 Ph AI~Q Qj Ph (-).(S)-1 H 2. Cyclomercuration of (+)-(R)-2 and (-)-(S)-2 with mercuric acetate and subsequent treatment with lithium chloride at room temperature gave two pairs of diastereomers, respectively. The four enantiopure compounds: (+) ?Rp,Rc)?, (? ?Sp,Rc)?, (+) ?Rp,Sc)?, (? ?(Sp, Sc) ? were isolated from the two mixtures by silica gel plate. 4 All of the compound 3 were characterized by elemental analyses, LR and 慔 NMR spectra. The structure and absolute configurations of the four diastereomers of compounds 3 were determined by x-ray diffraction. Hg Hg~OAc)2 K~N~C~Ph C?Ph 桺h CH3 ~ ?- Fe ~ + CH3 CH3 HgCI 鏗3 Ph %5~N桟桺l (I>? C桺h Hg(OAch H Fe Ph H (+)-(Rp, Sc)-3 3. Cyclopalladation of (+)-(R)-2 and (-)-(S)-2 with Li2PdCL~ in the presence of sodium abetate and subsequent treatment with PPh3 gave two pairs of diastereomers, respectively. The four enantiopure compounds: (+) -(Rp,Rc)-4, (-) -(Sp,Rc)-4, (+) -(Rp,Sc)-4, (-) -(Sp,Sc)-4 were isolated from the two mixtures by silica gel plate. All of the compounds 3 were characterized by elemental analyses, IR and 慔 NMR spectra. The structure and absolute configurations of the four diastereomers of compounds 4 were determined by x-ray diffraction or characterized by CD spectra. S (-)-(Sp, Sc)-3 PPh3 CI Ph Pd Li2PdCI4 Ph NaOAc 梸 Fe Ph CH3 PPh3 (+)-(Rp,Rc)-4 PPh3CI Pd 013 Ph / F (113 Li2RIa4 -~~N桟桺h Fe Ph NaOAc Fe Ph H H ~3 i;:::;~ (+)?Rp,Sc)? 113 (-)-(Sp,Rc) ?...