Natural Products Biosynthesis Involving a Putative Diels-Alder Reaction

The Diels-Alder cycloaddition is one of the most utilized reactions for the construction of cyclic systems with high regio-, chemo- and stereoselectivity. Accordingly, this versatile reaction has been broadly exploited in synthetic organic chemistry for the transformation of natural products, structurally diverse molecules of biological interests, pharmaceuticals, polymers and new materials. Nature has also used this cycloaddition reaction and Diels Alderase enzymes were proposed in many biosynthetic pathways of secondary metabolites. The aim of this account is to furnish to the scientific community an overview of reactions using a Diels Alderase for natural product biosynthesis. The proposed biosynthetic pathways involving Diels-Alder reaction are also summarized.