The growing relevance of biological ene reactions

Abstract

The ene reaction involves the addition of an 'ene' to an 'enophile.' The retro-ene reaction is the reverse of the ene reaction. In recent years various biological molecules have been found to form covalent intermediates (ene-adducts) that might be the result of an ene reactions. Such adducts have been characterized or implicated for dihydropyridines and pyridininum cofactors derived from vitamin B3, such as the reduced and oxidized forms of nicotinamide adenine dinucleotide (NADH/NAD); flavin cofactors derived from vitamin B2, such as flavin adenine dinucleotide, FAD, and flavin mononucleotide, FMN; vitamin C; the oxime intermediate of nitric oxide synthase; tyrosine; and other biomolecules. Given the ubiquitous nature of these cofactors, it might be speculated that the formation of ene-adducts is a more common principle in biochemistry.