Rearrangement Reaction Of Allylic α-aminonitrile

Rearrangement reaction is one of the most important classes of organic transformations, where the carbon skeleton of a molecule is rearranged to give a structural isomer of the original molecule. Due to the efficiency and atom economy, rearrangement reaction has received considerable attention from organic chemists.α-Aminonitriles are very useful and versatile intermediates in synthetic chemistry and have been widely used in the generation of multiple polyfunctional structures. However, the development of efficient rearrangement reaction of α-aminonitriles is less exploited. It this thesis, some rearrangement reaction of allylic α-aminonitrile have been studied.In the first part of the thesis, both Lewis base and thermo-initiated rearrangement of γ-allylic 1,2-dihydroisoquinolines have been developed, which provided β-allylic 1,2-dihydroisoquinolines with good functional group compatibility under the mild reaction conditions. In addition, the proposed mechanism was proposed on the basis of control experiments.In the second part, Cu-promoted cyclization of α-aminonitrile-tethered enynes incorporating electron deficient alkene component has been demonstrated. Several reaction parameters such as Lewis acids, temperature and solvents have been examined. Based on the preliminary investigation, a range of functionalized cyclopropanes were prepared efficiently.