Michael Addition Of Nitrodienynes And Construction Of Multifunctional Propargylamine Derivatives By Trapping Of Active Oxonium Ylide Intermediates

Michael addition reaction and Mannich-type reaction are two kinds of classic reactions which can construct carbon-carbon bond efficiently in organic synthesis,especially in fields of asymmetric addition.In this dissertation,asymmetric Michael addition of nitrodienynes and aldehydes in the present of organic catalysis was studied.Mannich-type reaction by trapping of active oxonium ylide intermediates in the presence of Rh2(OAc)4-Br(?)nsted acid was also studied.The dissertation was divided into four parts.In chapter 1,research progresses on the synthetic of a-Lycorane and organic catalytic asymmetric Mannich reaction between nitrodienynes and aldehydes were reviewed.The asymmetric catalytic conjugate addition of acetaldehyde to nitrodienynes or nitroenynes was studied,which can be applied on the synthesis of(+)-a-Lycorane and chiral P-alkynyl acids by a metal-free method.The asymmetric total synthesis of(+)-a-Lycorane was finished in 9 steps.In chapter 2,the recent research pregresses on electrophilic reagents trapping active oxonium ylide intermediates under the co-catalysis was reviewed.In 2014,our group first reported the synthetic methods of C-alkynyl N-Boc-protected N,O-acetals,which were the precursor of N-Boc alkynemine.This chapter can be divided into four parts:In part 1,using the C-alkynyl N-Boc-protected N,O-acetals and a-diazo carbonyl compounds,the Mannich-type reaction by trapping of active oxonium ylide intermediates in the presence of the catalysis of Rh2(OAc)4-Br(?)nsted acid was realized.By this reaction,a series of desired products were prepared with excellent diastereo-and enantioselectivity.In part 2,in the presence of co-catalysis,using the 3-diazooxindole and N,O-acetals,a series of multifunctional chiral P-alkynylamine derivatives containing 3,3'-disubstituted oxindoles skeleton were contructed.In part 3,the reaction of a-diazoacetate compounds and N,O-acetals was studied.It is an efficient approach to obtain chiral ?-amino-?-hydroxyesters,which were useful building blocks in bioactive natural products.In part 4,in the present of co-catalysis of Rh2(OAc)4-Br(?)nsted acid,Mannich-type reaction of C-aryl-N,O-acetal and a-diazo carbonyl compounds was realized.Based on above four parts,the possible reaction mechanism was proposed.Finally,the synthesized compounds were functionalized,which could prepare a series of P-amino alcohol derivatives.The chapter 3 included the summary and outlook of the dessertation.In chapter 4,the experimental procedures of chapter 1 and 2,as well as experimental datas for the new compounds were given.