Recent Advance in the Reductive Heck Cyclization for the Formation of Five to Nine Member Rings

Abstract: Palladium-catalyzed reactions are widely used for creating carbon-carbon and carbon-heteroatom bonds, with the Heck reaction being particularly valuable for forming rings of various sizes, including mediumsized rings. Recent reports have shown the synthetic potential of intramolecular Heck reactions for assembling rings of seven or more members. While the regioselectivity of this cyclization is often unpredictable in the absence of directing groups, the reductive Heck cyclization strategy can help minimize this issue. Nickel catalysts are also valuable due to their abundance and environmentally friendly nature, playing a pivotal role in producing biologically significant carbocycles and heterocycles. The use of both Pd(0) and Ni(0) catalysts, with or without chiral ligands, has been successful in forming five to nine-member ring heterocycles and carbocycles in a simple, cost-effective manner. This review provides a comprehensive survey of the literature from the past decade on the use of reductive Heck cyclization methodology, including mechanistic details as needed.