Synthesis, mechanism and applications of azido functionalized and α-imino carbene derived Tröger Bases

Tröger Bases (TB) are chiral bicyclic tertiary amines, which have drawn the interest of the synthetic organic community but only to a limited range of applications. In fact, the difficult functionalization of the main core of the molecule and the configurational lability of TB in acidic conditions have been two limiting factors. The aim of this PhD was to develop synthetic methodologies to overcome these two drawbacks. Therefore, an efficient protocol of C-H functionalization at the benzylic positions was developed to give access to versatile mono- and bis-azido TB derivatives. This allowed the access to a new class of functional anion binding catalysts. Additionally, while exploring the reactivity of N-sulfonyl-1,2,3-triazoles with TB in the aim of synthetizing configurationally stable derivatives via N-ylide chemistry, a route to novel polycyclic indoline-benzodiazepine scaffold was discovered. Through an original cascade of [1,2]-Stevens rearrangement, Friedel-Crafts, Grob fragmentation and aminal formation reactions, polycyclic 5,6,7-membered heterocycles were obtained in good yields and complete diastereoselectivity