One pot synthesis of maleimide and hydantoin by Fe(CO) 5 catalyzed [2 + 2 + 1] co-cyclization of acetylene, isocyanate and CO

Abstract

In the presence of a catalytic amount of Fe(CO) 5, terminal acetylenes, isocyanates and CO undergo [2 + 2 + 1] cyclization to form substituted maleimides and hydantoins; when internal alkynes are used, exclusive maleimide formation is observed. While the maleimides can be obtained as the major products, in up to 90% yield, when the reaction is carried out in CO atmosphere, in absence of CO, the hydantoins are formed in up to 87% yield. Formation of maleimides has been shown to occur via the formation of a ferrole intermediate, whereas the hydantoins are proposed to form through successive insertion of isocyanate into the iron-acetylide bond. All compounds were characterized by spectroscopic methods and molecular structures of some compounds were established by single crystal X-ray diffraction method. © The Royal Society of Chemistry 2012.