Klas Kimberly, Tsukamoto Sachiko, Sherman David H, Williams Robert M
Department of Chemistry, Colorado State University , Fort Collins, Colorado 80524, United States.
Graduate School of Pharmaceutical Sciences, Kumamoto University , 5-1 Oe-honmachi, Kumamoto 862-0973, Japan.
J Org Chem. 2015 Dec 4;80(23):11672-85. doi: 10.1021/acs.joc.5b01951.
Eight examples of biosynthetic pathways wherein a natural enzyme has been identified and claimed to function as a catalyst for the [4 + 2] cycloaddition reaction, namely, Diels-Alderases, are briefly reviewed. These are discussed in the context of the mechanistic challenges associated with the technical difficulty of proving that the net formal [4 + 2] cycloaddition under study indeed proceeds through a synchronous mechanism and that the putative biosynthetic enzyme deploys the pericyclic transition state required for a Diels-Alder cycloaddition reaction.
简要回顾了已鉴定出天然酶并声称其作为[4 + 2]环加成反应催化剂(即双烯加成酶)的生物合成途径的八个例子。这些例子是在与技术难题相关的机制挑战的背景下进行讨论的,这些技术难题在于证明所研究的净形式[4 + 2]环加成确实通过同步机制进行,以及假定的生物合成酶采用双烯加成环加成反应所需的周环过渡态。