Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Hokkaido, Japan.
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Hokkaido, Japan.
J Org Chem. 2021 Nov 5;86(21):15597-15605. doi: 10.1021/acs.joc.1c02108. Epub 2021 Oct 21.
Chloropupukeananin, chloropupukeanolides, and chloropestolides are a family of structurally complex bioactive natural products that possess highly functionalized tricyclo[4.3.1.0]decane or bicyclo[2.2.2]octane skeletons. Biosynthesis of the chloropupukeananin family is triggered by the intermolecular heterodimeric Diels-Alder reaction between maldoxin and iso-A82775C; however, the enzymes involved have not yet been identified. We herein report the one-pot biomimetic synthesis of chloropupukeananin and chloropupukeanolide D. Moreover, the effect of the solvent on the intermolecular Diels-Alder reaction of siccayne and maldoxin suggested that the biosynthesis of the chloropupukeananin family involves a Diels-Alderase-catalyzed heterodimeric Diels-Alder reaction.
氯棕酮烷类、氯棕酮醇类和氯棕酮内酯类是一类结构复杂的生物活性天然产物，具有高度官能化的三环[4.3.1.0]癸烷或二环[2.2.2]辛烷骨架。氯棕酮烷类的生物合成是由 maldoxin 和 iso-A82775C 之间的分子间杂二聚 Diels-Alder 反应触发的；然而，参与的酶尚未被鉴定。本文报道了氯棕酮烷类和氯棕酮醇类 D 的一锅仿生合成。此外，溶剂对 siccayne 和 maldoxin 之间的分子间 Diels-Alder 反应的影响表明，氯棕酮烷类的生物合成涉及 Diels-Alderase 催化的杂二聚 Diels-Alder 反应。
