Asymmetric Synthesis Of ?,?-Disubstituted ?-Amino Acids And Benzo-1,4-diazepino[1,2-a]Indoles Catalyzed By Pd-Complexes

Asymmetric catalysis of transition metals has played an important role in organic synthesis.In this paper,the reactions involved by palladium-complexes catalyzed the formation of an allylic systems into a ?-Pd-allyl zwitzonic intermediate were expanded.There are three parts for this thesis:Chapter 1.This chapter reviews the reactions of ?-pd-allyl zwitterionic intermediates catalyzed by transition metals from vinyl benzoxazinones.The reactions including asymmetric substitution,cyclization reaction and C-H activation reaction involving different reaction sites of ?-pd-allyl zwitterionic intermediates.Chapter 2.We have developed an efficient Palladium-complexes catalyzed AAA reaction of azlactones and vinyl benzoxazinones for the synthesis of functionalized allylate azlactones derivatives in good yield with excellent regioselectivity and enantioselectivities.The chiral ?,?-disubstituted ?-amino acid derivatives were obtained by ring-opening reaction in methanol.And with the combination of p-benzoquinone,it was successfully converted into chiral ?-amino acid derivatives with indole-2-methyl substitution.It has provided a new method for the synthesis of chiral ?,?-disubstituted ?-amino acid.Chapter 3.We have disclosed palladium-complexes catalyzed decarboxylative asymmetric [4+3] cyclization of N-free vinyl benzoxazinones and indole-2-formaldehyde to obtained chiral Benzo-1,4-diazepino[1,2-a]indoles in good yield with good enantioselectivities.This reaction has good substrate suitability and provided a new method for the synthesis of chiral benzo-1,4-diazepino[1,2-a]indoles.