| Asymmetric catalysis is a flexible and effective method in the preparation of enantiomerically rich compounds. Great progress in this field has been made by using catalysts based on transition metal complexes modified by chiral ligands. Starting with some chiral ferrocenyl intermediates containing a diphenylphosphino moiety and a primary or a secondary amino moiety, many ferrocene based phosphine-amidine, phosphine-imine, phosphine-triazine and diphosphine ligands were synthesized. The application of these chiral ferrocene based ligands in Pd-catalyzed asymmetric allylic substitutation was carried out.1. Synthesis of ferrocenyl phosphine-amine intermediates with active primary (P-I -- P-IV) or secondary amino moiety (P-V-P-IX)1) Using acylferrocene as the starting materials, 3 chiral ferrocenyl phosphine-primary amines (R)-S5p)-PPFNH2-R (P-I~P-III) and 5 chiral ferrocenyl phosphine-secondary amines (R)-(SP)-PPFNHR (P-V~P-IX) intermediates have been prepared in enantiopure form by stereoselective multistep synthesis. Among them, P-II, P-III, P-VII, P-VIII and P-IX are new compounds.2) In order to investigate the role of planar chirality in the following research,the synthesis of (S)-(Sp)-PPFNH2, a diastereoisomer of (R)-(Sp)-PPFNH2, was attempted. Through introduction of a trimethylsilyl as a protected group at the initial step in the synthesis, an effective method in the preparation of enantiomerically pure (S)-(Sp)-PPFNH2 was developed from an important precusor - (S)-1-[(S)-2-trmiethylsilyl-(R)-5-diphenylphosphino]ferrocenyl]ethylamine(P-IV).2. Synthesis of chiral ferrocenylphosphine-amidine, phosphine-imine, phosphine-triazine and diphosphine ligandsStarting with chiral ferrocenyl phosphine-primary amines (P-I~P-in), three families of chiral ferrocenyl P,N ligands were designed and synthesized, which included 8 ferrocenylphosphine-amidines (A-l~A-8), 19 ferrocenylphosphine-imines (B-1~B-19) and a chiral ferrocenylphospnine-amide ligand C-1. Except for B-1 and B-11, all of these chiral ligands are new compounds. Derived from chiral ferrocenyl phosphine-secondary amine (P-V~P-IX), 8 novel ferrocenylphosphine-triazine ligands and a novel chiral bis(ferrocenyl)P2N ligand E-l with C2-symmetry were synthesized.In order to synthesize the target ligands, some new synthetic methods were used. 1) An effective method hi the preparation of ferrocenylphosphine-imine ligands from amines (P-I~P-n) and mono-substituted acetophenones was developed. In the presence of active A^Oa and anhydrous MgSO4, the ferrocenylphosphine-unine ligands (B-14~B-19) can be synthesized in good yields. 2) In the presence of a new condensing agent DMTMM, the chiral amide ligand C-1 was easily derived from ferrocenylphosphine-primary amines and 2-pyridinecarboxylic acid. 3) A novel effective method was developed to synthesize Knochel's ferrocene based diphosphine ligand F-l by the lithiation and phosphinylation of PPFA-Ph 4.3. Pd-catatyzed asymmetric allylic substitution using chiral ferrocene based P,N ligands and diphosphine ligandsThe application of new developed P,N ligands (A, B, C and D) and diphosphines (E and F) in Pd-catalyzed asymmetric allylic alkylation of l,3-diphenylprop-2-en-l-yl acetate or pivalate with dimethyl malonate was investigated. 1) chiral ferrocenylphosphine-amiduie ligands (A) proved highly effective in this asymmetric transformation, and up to 96% ee with 98% yield was obtained by use of ligand A-4. 2) chiral ferrocenylphosphine-imine ligands (B) proved highly effective in this asymmetric transformation, and up to 98% ee with 95% yield was obtained by use of ligand B-19. The substituted effects of phosphine-imine ligands (B) on the catalytic reaction was investigated and found that ligands with meta-electron-withdrawing substitution tended to give higher catalytic activity and enantio selectivity. 3) In these two kinds of ferrocene based P,N ligands, the planar chirality have the predominated role in the asymmetric reaction. Through matching the (R)-central configuration and (Sp)-planar...
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