title: Mechanistic insights into Diels-Alder reactions in natural product biosynthesis.
abstract: Natural enzymes that catalyze Diels-Alder reactions have long been sought after, yet few enzymes have been experimentally confirmed to perform this reaction. In the past five years, several stand-alone enzymes that can catalyze the Diels-Alder reaction had been identified and characterized. Among which, the crystal structures of SpnF, PyrI4 and AbyU have been determined. The structures of PyrI4 and AbyU, which are involved in spirotetronate/spirotetramate biosynthesis, are particularly informative since they shed light on how a natural catalyst captures the flexible substrate and facilitates the intramolecular Diels-Alder reaction through stabilization of the transition state in catalysis. These pioneering studies will inspire the design of artificial catalysts for Diels-Alder reactions.
authors.affiliation: National Institute of Advanced Industrial Science and Technology (AIST), 2-4-7 Aomi, Koto-ku, Tokyo 135-0064, Japan.
authors.forename: Takuya
authors.initials: T
authors.lastname: Hashimoto
authors.affiliation: Biotechnology Research Center, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan. Electronic address: utkuz@mail.ecc.u-tokyo.ac.jp.
authors.forename: Tomohisa
authors.initials: T
authors.lastname: Kuzuyama
mesh_terms: D000595:Amino Acid Sequence; D001688:Biological Products / Q000737:chemistry / Q000378:metabolism*; D018360:Crystallography, X-Ray; D061565:Cycloaddition Reaction; D004798:Enzymes / Q000737:chemistry / Q000378:metabolism; D011487:Protein Conformation; D017386:Sequence Homology, Amino Acid
chemical_list: D001688:Biological Products; D004798:Enzymes