Silylium ion mediated 2+2 cycloaddition leads to 4+2 Diels-Alder reaction products

The mechanism of silver(I) and copper(I) catalyzed cycloaddition between 1,2-diazines and siloxy alkynes remains controversial. Here we explore the mechanism of this reaction with density functional theory. Our calculations show that the reaction takes place through a metal (Ag(+), Cu(+)) catalyzed [2+2] cycloaddition pathway and the migration of a silylium ion [triisopropylsilyl ion (TIPS(+))] further controls the reconstruction of four-member ring to give the final product. The lower barrier of this silylium ion mediated [2+2] cycloaddition mechanism (SMC) indicates that well-controlled [2+2] cycloaddition can obtain some poorly-accessible IEDDA (inverse-electron demand Diels-Alder reaction) products. Strong interaction of d(10) metals (Ag(+), Cu(+)) and alkenes activates the high acidity silylium ion (TIPS(+)) in situ. This п-acid (Ag(+), Cu(+)) and hard acid (TIPS(+)) exchange scheme will be instructive in silylium ion chemistry. Our calculations not only provide a scheme to design IEDDA catalysts but also imply a concise way to synthesise 1,2-dinitrogen substituted cyclooctatetraenes (1,2-NCOTs).