Chemistry
Name: Advanced Physical Organic Chemistry
Catalog Number: 411001Y Hours/Credits: 40/2
Prerequisite(s):
Organic Chemistry, Physical Chemistry, Quantum Chemistry (partial) Course Level: Basic discipline course for graduates in chemistry
Course Description:
The graduate students are required to study the structures, properties and the reaction mechanisms of organic compounds by using the theory, concepts and methods obtained from the organic chemistry and physical chemistry for undergraduate. From the perspective of molecular orbital theory, kinetic, stereochemistry, media effects and organic reactive intermediates to study the correlation of the reaction mechanism. In the way of the step-by-step vs. the concerted reaction, from the ground state to excited states to discuss the different reaction mechanisms. Its purpose is to let the graduates to achieve a better understanding of how the complicated organic chemistry reaction occurs (Why), and to connect the theory with the future researches. Combining the group study and the reviews on the recent literatures related to reactions corresponding to each chapter, the students can understand the cutting-edge research results, find the problem to be resolved, try to present new research content, and learn to suggest research questions plus to analyses the comprehensive experimental data, to draw the appropriate conclusions by the scientific method, on the one hand, can improve the abilities for independent thinking and problem-solving skills, as well cultivate the spirit of cooperation.
Course Content:
Chapter 1 Organic reaction transition state and the energy and mechanism theory Study the reaction mechanism and related theoretical issues: the transition state theory, hypothesis of Hammond, Curtin, Hammett principle, the kinetic isotope effect and substitute effect, strain force effect. conjugated effect, spiroconjugation effect, anomeric effect, hyperconjugation, and effect of homoconjugation Chapter 2 Medium effects Polarity of the solvent, ion pair, hydrophobic and hydrophilic effects, lipophilic or lipophobic effects, medium acidity and reaction mechanism, soft-hard acids or bases. Chapter 3 Stereochemistry Stereochemistry in chemical reaction, chirality and chiral separation, the application of spectroscopic methods (NMR, IR, UV, MS, CD, ORD) in the stereochemistry study, stereochemistry in supramolecules. Chapter 4 Pericyclic （electrocyclic） reaction & concerted reaction Concerted reaction, electrophilic cyclization reaction, cycloaddition and ring elimination reaction, σ-migration; ene reaction, cheletropic reaction, Mobius-Hückel rings & rules, Frontier molecular orbitals & the Woodward-Hoffmann rules, and their applications in chemical synthesis. Chapter 5 Organic Reaction intermediates and research methods Carbocations, carbanions, free radicals, ion radicals( cation radical, anion radical), carbene, nitrene, benzyne, and their structures and reactivities. Chapter 6 Catalytic reaction and mechanism Catalytic hydrogenation, catalytic oxidation, catalytic carbonylation, catalytic polymerization, enzyme catalysis. Chapter 7 Organic photochemistry and electrochemistry excitation and excited state, deactivation and energy transfer of excitation state, photochemistry of carbonyl compounds, ene and diene photochemistry, electron transfer, the anode reaction, cathode reaction.
TextBooks:
1)Yun-Yang Wei, Jian Li, Introduction to the chemical reaction mechanism, the Science Press, Beijing, 2004; 2) Xiu-Lin Ye, Stereochemistry, Peking University Press, Beijing, 2001; 3) Xiang-Yu Sun, Introduction to Theoretical Organic Chemistry, Chinese Academy of Sciences, Graduate University of the Department of Chemistry, 1994.7;
Reference:
1) Eric V Anslyn, Dennis A. Dougherty, Modern Physical Organic Chemistry, University of Science Books, 2006. (ISBN: 1-891389-31-9); (Chinese version, translated by Guo-zheng Ji, Zhen-He Tong, Modern Physical Organic Chemistry, Higher Education Press, 2009.) 2) Rong-Bao Wei , Xu-Bin He, Qi Ou et al. Organic conjugated effect and the anomeric effect, Science Press, 2008. 3)Zhen-Heng Gao, Physical Organic Chemistry, Higher Education Press, 1983.