Palladium(0)/palladium(II) catalysed C(sp3)-H activation : from direct to remote functionalization

Abstract

Over the past decades, the transition metal-catalysed intramolecular activation of unactivated C-H bonds has emerged as a powerful tool for organic chemists according to the abundance of such bonds. Selective functionalizations of C-H bonds provide a rapid access to molecular complexity in an atom- and step-economical fashion. The research in our group is centered on the activation and functionalization of C(sp3)-H bonds that lead to the development of new methodologies and applications including asymmetric catalysis, mechanistic studies and total synthesis of natural products. Within this field, my Ph.D. thesis was focused on the development of new methodologies involving Pd0/PdII catalysed C(sp3)-H activation to access valuable heterocyclics building blocks or natural products. My thesis is divided into two distinct parts, namely “direct C(sp3)-H functionalization” and “remote C(sp3)-H functionalization”. In the first part of this thesis, we present the synthesis of lycorine alkaloids, in an elegant and straightforward manner. Then, we propose a new synthesis of B-lactams,using carbamoylation reaction. The last chapter of this part is focusing on the synthesis of benzoxazine, after benzazetidine rearrangement. In the second part of this thesis, we developed new synthetic methods for the remote functionalization of distal C-H bonds. First, the synthesis of G-lactams and indanones after palladium migration. Then, the synthesis of benzofurans, indolines and chromanones using a similar methodology.