Contents

1. Abstract 2. Introduction 3. General Description 4. Structure of Oxoalkyne, Auric-ate Complex (Scheme2) 6. Proposed Reaction Mechanism (Scheme3) 7. Computational Details 8. Result and Discussion 9. Optimized structure of Auric-ate complex (Figure 5) 10. Energy difference between HOMO and LUMO (Table 1) 11. Frontier Molecular Orbital (Scheme4) 12. Conclusion and Outlook 13. References and Notes 2 3 4 5 7 8 9 11 12 15 16 16

Abstract

The relation between structure and function has become a model for chemistry and biochemistry, and thus theoretical studies of the electronic structure of Au provide insight a priori into how it might function as a catalyst and what reactive pathways might be accessible. The Aucl3-catalyzed benzannulation of pyridine containing oxo-alkynes with external as well internal alkynes proceeds under mild conditions, and a variety of quinoline and isoquinoline derivatives are produced in good to excellent yields. The reaction proceeds through the formation of aza-isobenzopyrylium auric ate complex. In BP86 mechanistic study the electron rich auric ate complex react effectively with electron poor dienophiles to yield variously substituted quinolines/isoquinolines in good to high yields. On the other hand electron rich auric ate complex does not react with electron rich dienophiles and vice versa. This observation invoke the Diels-Alder type [4+2] cycloaddition. This confirms that the reaction requires a proper HOMO-LUMO matching. The smaller the energy difference between these frontier orbitals, better these orbitals interact and therefore the more readily the reaction occurs.