Aryne-Mediated [2,3]-Sigmatropic Rearrangement Of Tertiary Allylic Amines

Aryne, as a highly reactive intermediate, can react with a variety of nucleophiles under mild conditions to construct carbon-carbon bond and carbon-hetero atom bond, and thus has great value in organic synthesis. Based on the nucleophilic attack capability of tertiary amines to aryne, we developed the aryne-mediated [2, 3]-sigmatropic rearrangement of tertiary allylic amines.This dissertation includes two chapters.Chapter 1:Progress in aryneFirstly, this chapter describes the preparation and properties of aryne; then intruduces the reactions of aryne participated mainly from four aspects, in these four areas, insertion and cycloaddition reaction of aryne have been widely studied, which can construct carbon-carbon bonds, carbon-hetero bonds and heterocycles efficiently; Compared with the previous two, the multicomponent reaction of aryne is developed later, but showed great potential; Finally, the reactions of aryne with benzene sulfinate, dialkyl sulfoxides and sulfoxides imines are undoubtedly a great expansion.Chapter 2:Aryne-mediated [2,3]-sigmatropic rearrangement of allylic tertiary amines.Allylic ammonium ylides can be generated by N-alkylation of tertiary amine or metal carbenoid-mediated coupling between tertiary allylic amines and diazo compounds and as well palladium-catalyzed N-alkylation of tertiary amines with allylic carbonates. Meanwhile, aryne can react with tertiary amines and then lead to rearrangement, ring expansion reaction and so on. We redesigned the structure of tertiary allylic amine and found that it could react with aryne under room temperature to give homoallylic amines with good yield, and the reaction could tolerate a series of functional group such as ester, ketone, amide, cyano, phosphonate, and even for some different substituents on double bond and nitrogen atom also had a good compatibility. Either L,-proline derivative or L-pipecolinic acid derivative also showed a good chirality transfer. Finally, a series of derivations of the obtained homoallylic amines were studied.