Allosteric Cofacial Porphyrin Complexes超分子变构cofacial卟啉配合物ppt课件.pptVIP

Supramolecular Allosteric Cofacial Porphyrin Complexes;Allosteric Recognition;Introduction-Porphyrin;;Holliday, B. J. et. al. Angew. Chem. Int. Ed. 2001, 40, 2022-2043.;The Directional-Bonding Approach;The Symmetry-Interaction Approach;The Weak-Link Approach;Catalytic Acyl Transfer by a Cyclic Porphyrin Trimer;Design of Allosteric Porphyrin-Based Supramolecules;( i ) 1-bromo-2-chloroethane, K2CO3, Acetone, Reflux ( ii) 1,3-propanedithiol, Y(OTf)3 (5 mol %), CH3CN (iii) KPPh2, THF (iv) S8, THF ( v) NaNO2,AcCl/H2O, CH2Cl2, 0 °C → rt;( vi ) 5-mesityldipyrromethane, BF3?OEt2, DDQ, NEt3, CHCl3, 4 ? Molecular Sieves (vii ) Zn(OAc)2?2H2O, 4:1 CHCl3/MeOH, Reflux (viii) Cp2ZrHCl, THF, 60 °C;(ix) [Rh(CO)2(Cl)]2, CH2Cl2/THF ( x) [Cu(CH3CN)4]PF6, CH2Cl2/THF;X-ray crystal structure of 8a?DABCO as viewed (A) from the side and (B) from the top;X-ray crystal structure of 8c?DABCO as viewed (A) from the side and (B) from the top;( i ) ClCH2CH2PPh2, Cs2CO3, CH3CN, Reflux ( ii) S8, THF (iii) n-BuLi, DMF, THF, -78 °C 5-mesityldipyrromethane, BF3?OEt2, DDQ, NEt3,CHCl3, 4 ? Molecular Sieves;( v ) Zn(OAc)2?2H2O, 4:1 CHCl3/MeOH, Reflux ( vi ) Cp2ZrHCl, THF, 60 °C ( vii) for 14a: [Rh(NBD)Cl]2, AgBF4, CH2Cl2/THF (viii) for 14b: [Cu(CH3CN)4]PF6, CH2Cl2/THF;(ix) for 15a: PPNCl/CO (1 atm) ( x) for 15b: C5D5N.;NMR Data of 14a and 14b;X-ray crystal structure of 15a?DABCO as viewed (A) from the side and (B) from the top;X-ray crystal structure of 15c?DABCO as viewed (A) from the side and (B) from the top;Closed macrocycle;Formation of 4-(acetoxymethyl)pyridine (4-AMP) plotted as concentration vs. time for 14a and 15a.;Formation of 4-(acetoxymethyl)pyridine (4-AMP) plotted as concentration vs. time for [Zn(TPP) + 16a] and [Zn(TPP) + 16b];Catalytic efficiency of 4-PC;Formation of 3-(acetoxymethyl)pyridine (3-AMP) plotted as concentration vs. time for 14a and 15a.;Formation of 3-(acetoxymethyl)pyridine (3-AMP) plotted as concentration vs. time for