物理有机化学PPT-复旦大学-王全瑞 4.catalyst by acid and base.ppt

* Sc3+-Catalyzed Aldol-Type Additions of N-Benzoylcyclopropanecarboxamides via Iodide-Mediated Ring-Opening: Stereoselective Synthesis of ?-Lactams * Postulated catalytic cycle Summary:Advantages of Metal Ions Compared to H+ Higher charge (M2+, M3+) Also works at neutral pH Coordination with several groups is possible (template effect) Many metal ions have redox properties * Catalysis by Acids, Bases and Metal Ions Mechanism: 1) The diffusion-controlled formation of a hydrogen bond between the base B– and the acid HA 2) The transfer of a proton, leading to the formation of a new hydrogen bonded complex 3) The diffusion-controlled dissociation of the product The rate of proton transfer * proton transfer to N, O, S is fast; proton transfer to carbon (C) is slow proton transfer from H3O+ to N or O is diffusion-controlled: k-1 ? 1011 l.mol-1.s-1 Formation of the hydrogen bond between the proton donor and the proton acceptor is the rate determining step: this step is slower than the actual proton transfer! Typical for cases where a proton is both bound to and transferred to oxygen or nitrogen atoms, where the negative charge is localized on one atom. * Nevertheless, diffusion of H+ in water is much faster than diffusion of other ions: * Proton Transfer from/to Carbon Acids/Bases k1 = 4x10 － 8 l.mol －1.s－1, slow process due to: - lack of hydrogen bond formation before proton transfer - low acidity of the hydrogen atoms. k-1 = 16 l.mol －1.s－1, also much slower than diffusion rate, because: - upon protonation a considerable redistribution of charge has to take place, including the concomitant change of solvation. 1 2: carbon acid, k1 and k-1 relatively small 2 3: oxygen acid, k1 and k-1 relatively large (H-bond formation) Another example: * * Most carbon acids are stabilized by resonance. Hence significant structural reorganization must accompany deprotonation The greater the structural reorganization during deprotonation, the lower the kinetic acidity Inf