Study on the mechanism of intra- and intermolecular benzannulation reaction of the fischer carbene complexes with alkynes.

摘要

Chapter 1 introduces some methods of electronic structure calculations and analysis as applied to transition metal carbene complexes.;Chapter 2 outlines the "complete" potential energy surface along the benzannulation reaction coordinate for prototypical Fischer carbene complex (CO)5Cr=C(OH)CH=CH2 and HCCH.;Chapter 3 discusses the mechanistic aspects of benzannulation reaction of functionalized alkynes through the prism of the correlation analysis on calculated barriers with DFT methods.;Chapter 4 is dedicated to the intramolecular and asymmetric versions of the benzannulation reaction and synthesis of chiral metacyclophanes. Theoretical study supplements and rationalizes the experimental results. The synthesis and application of new organocopper reagents for one- and two-carbon chain extension is described.;Chapter 5 summarizes the experimental procedures and compiles the compounds characterization data.