DFT studies on four different kinds of copper‒catalyzed carbon‒carbon bond formations reactions (namely, aza‒Diels‒Alder cycloaddition reaction, deoxygenation of epoxides, difunctionalization of 1,3‒enynes and 1,3‒dipolar cycloaddition reaction) are reported. The detailed reaction mechanisms and stereoselectivities have been explored.

Chapter 1 gave a short introduction to DFT calculations, copper‒catlayzed carbon‒carbon bond formation reactions and cycloaddition reactions. Chapter 2 dealt with the aza‒Diels‒Alder cycloaddition reaction. Different pathways were calculated and it was found that the reaction proceeded by the inverse Diels-Alder reaction pathway. Moreover, the diastereoselectitivy and enantioselectivity were explained. Chapter 3 was about the deoxygenation of epox...[ Read more ]

DFT studies on four different kinds of copper‒catalyzed carbon‒carbon bond formations reactions (namely, aza‒Diels‒Alder cycloaddition reaction, deoxygenation of epoxides, difunctionalization of 1,3‒enynes and 1,3‒dipolar cycloaddition reaction) are reported. The detailed reaction mechanisms and stereoselectivities have been explored.

Chapter 1 gave a short introduction to DFT calculations, copper‒catlayzed carbon‒carbon bond formation reactions and cycloaddition reactions. Chapter 2 dealt with the aza‒Diels‒Alder cycloaddition reaction. Different pathways were calculated and it was found that the reaction proceeded by the inverse Diels-Alder reaction pathway. Moreover, the diastereoselectitivy and enantioselectivity were explained. Chapter 3 was about the deoxygenation of epoxides, three possible pathways were proposed and the pathway via the oxonium ylide intermediates was favored. Chapter 4 dealt with the difunctionalization of 1,3‒enynes. Reaction mechanisms involving the divergence were studied by DFT calculations. And the reasons leading to the 1,2/1,4‒addition selectivites were explained. Chapter 5 dealt with the 1,3‒dipolar cycloaddition reaction. The regioselectivity due to the change of substrates were explored. It was found that the [3+2] cycloaddition product was the kinetic product while the [3+6] product was the thermodynamic product. The change of substrates led to the change in free energies of overall transition states and intermediates. Therefore, when an ester‒substituted dipolarophile was used, the kinetic product was formed. While the ester‒substitutent was changed to the keto‒substitutent, the thermodynamic product was formed. Finally, a short summary and personal outlook was given in chapter 6.