Construction of heterocyclic rings from cyclopropenes

Abstract

Heterocyclic rings are the fundamental building blocks of biological systems and have wide applications in synthetic chemistry and medicinal science. The development of novel synthetic methodology for heterocyclic skeletons from a variety of starting materials has made great progress in the past decades. Meanwhile, highly strained cyclopropenes as reactive reagents in organic transformations have drawn much attention from chemists. The rich chemical reactivity and reaction routes have been well investigated, and some review articles related to the reactivity of cyclopropenes and the construction of carbocycles and acyclic compounds have appeared in these years. Thus, this review mainly focuses on the progress in the construction of heterocyclic rings starting from various cyclopropenes including the reactions of commonly available stable cyclopropenes, in situ generated reactive cyclopropenes and cyclopropene precursors during this decade. Firstly, the transformations of common cyclopropenes into donor-type vinyl metal carbenes via transition metal induced ring opening, direct metalation of the CC bond of metal complexes, and cycloaddition reactions with 1,3-dipoles are described. Next, the annulation reactions of reactive cyclopropenes generated in situ with donor–acceptor reagents, intramolecular nucleophilic addition, and the cycloaddition reactions with 1,3-dipoles are introduced. Then, the transformation of cyclopropene precursors such as alkyl 1-chloro- or 1-alkoxy-2-aroylcyclopropanecarboxylates into five-membered heteroaromatic compounds is also mentioned. In addition, a brief outlook of the opportunity and challenges in the field of bio-orthogonal reactions related to cyclopropenes is given.