RESUMO
We present a computational mechanistic study on the copper(III)-catalysed carboarylation-ring closure reactions leading to the formation of functionalised heterocycles. We have performed DFT calculations along selected routes and compared their free energy profiles. The calculations considered two viable options for the underlying mechanism which differ in the order of the oxazoline ring formation and the aryl transfer steps. In our model transformation, it was found that the reaction generally features the aryl transfer-ring closing sequence and this sequence shows very limited sensitivity to the variation of the substituent of the reactants. On the basis of the mechanism the origin of the stereoselectivity is ascribed to the interaction of the Cu ion with the oxazoline oxygen driving the ring-closure step selectively.
RESUMO
A copper-catalyzed carboarylation-ring-closure strategy was used for the modular synthesis of oxazolines via the reaction of 1-aryl- and 1-alkylpropargylamides and diaryliodonium salts. The novel approach enables the efficient, modular synthesis of oxazoline derivatives bearing fully substituted exo double bonds.
RESUMO
A new copper-catalyzed oxidative ring closure of ethynyl anilides with diaryliodonium salts was developed for the highly modular construction of benzoxazines bearing a fully substituted exo double bond. The oxidative transformation includes an unusual 6-exo-dig cyclization step with the formation of C-O and C-C bonds.