RESUMO
The mechanism of a trinuclear cooperative dehydrogenative C-N bond-forming reaction is investigated in this work, which avoids the use of chelate-assisting directing groups. Two new highly efficient Ru/Cu co-catalyzed systems were identified, allowing orders of magnitude greater TOFs than the previous state of the art. In-depth kinetic studies were performed in combination with advanced DFT calculations, which reveal a decisive rate-determining trinuclear Ru-Cu cooperative reductive elimination step (CRE).
RESUMO
The Ru catalyzed cross-dehydrogenative C-O bond formation between anilines and phenols is described and discussed. The exclusive C-O versus C-N bond-formation selectivity, moreover in the absence of chelating-assisting directing groups and while leaving the N-H position untouched, is a remarkable feature of this metal-catalyzed radical cross-dehydrogenative coupling.
RESUMO
Highly π-extended hetero-cyclic/aromatic skeletons are of great importance as they can be utilized in many organic material based technologies. Therefore, developing efficient, pre-activation-free, synthetic procedures for the rapid build-up of these complex structures remains a high priority objective. The herein presented approach delivers highly fused carbazole skeletons from simple naphthylamine derivatives.