Recent Advances in [5+2] Cycloadditions

Abstract: The existence of a seven-membered cyclic core in several natural products and biomolecules vitalized the research on its synthesis. [5+2] cycloaddition has become a promising strategy for the construction of seven-membered ring systems by the formation of carboncarbon bonds in a single step, with strong regioselectivity and stereoselectivity. This review mainly focuses on recent developments in the area of [5+2] cycloaddition since 2019. Total synthesis of natural products involving [5+2] cycloaddition as a key step leading to the heptacyclic core has also been discussed. Synthesis of fused and bridged ring systems via the reactions involving inter and intramolecular [5+2] cycloadditions like oxidopyrylium-mediated [5+2] cycloadditions, [5+2] cycloadditions of vinyl cyclopropanes (VCPs), vinyl phenols, etc. is explained in the review with the latest examples. This review provides a useful guide for researchers exploring this powerful strategy to create more elegant heptacycles in their future research.