Density functional theory (DFT) calculations were utilized to reveal the effect of highly efficient transition metal catalysis in inverse electron demand Diels‐Alder (IEDDA) reactions. The silver‐catalyzed IEDDA reactions of 1,2‐diazines and siloxy alkynes were investigated to highlight the effect of the catalyst and its mode of action. Two different reaction pathways, concerted and stepwise, were explored as well as the uncatalyzed reaction. Computations elucidate the details of the highly efficient Ag catalyst in IEDDA reaction, and are consistent with previous experimental studies. The mode of action for the catalyst is fully revealed and its specific effect on the regioselectivity/specificity of the reaction is established.

A series of novel indoline-(thio)urea were designed and prepared using indoline(s) as a new platform and tested as organocatalysts in the Michael and Morita-Baylis-Hillman reactions. Most of the compounds were found to be very active catalysts although they did not promote the enantioselectivity. As agents for the conversion of thiocarbonyl compounds into carbonyl compounds, potentials of PIFA and DDQ were also displayed. Furthermore, DFT calculations rationalized the experimentally observed non-enantioselectivity of the catalysts.