Novel Halogen(I) Reagents in the Csp2- and Csp3-Bond Functionalization

The work presented in this thesis represents some major developments in halogen(I) reagents, specifically towards     the functionalization of C(sp2)-H and C(sp3)-H bonds through iodine(I)- and bromine(I)-reagents.

The present manuscript is divided into three principal parts:

1- Iodine(I) reagents for vicinal alkene difunctionalization

2- Oxidative amination of C-(sp3)-H bonds of tetrahydrocarbazoles

3- Application of iodine(I) reagent or bromine catalysis to the formal synthesis of (±)-aspidospermidine.

In the first section on alkene difunctionalization, we have presented a general synthesis, isolation and characterization of several novel iodine(I) reagents with the formula R4N[I(O2CAr)2]. These compounds exhibit high air and moisture stability. We were interested in the exploration of reactions promoted by electro-philic iodine towards a vicinal iodooxy-genation of styrene derivatives.

In the second section an exploration of the use of Varvoglis reagent PhI(NPhth)2 has been carried out. This reagent was used to the synthesis of iodine(I) and bromine(I) reagents with phthalimide ligands to stabilize the electrophilic halogen center. As oxidative amination of tetrahydrocarbazoles in position 4 has not been explored so far, we developed an innovative methodology to carryout the C(sp3) oxidative amination of tetrahydrocarbazole derivatives using iodi-ne(I) reagent or bromine catalysis.

Finally, in the third chapter we wanted to demonstrate the versatility and performance of halogen reagents described in the previous chapter, which were used in the synthesis of (±)-aspidospermidine