Department of Chemistry, University of California, Berkeley, 826 Latimer Hall, Berkeley, CA, 94720, USA.
Department of Chemistry, Yale University, 275 Prospect Street, New Haven, CT, 06520, USA.
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12498-12502. doi: 10.1002/anie.201705654. Epub 2017 Aug 30.
Meroterpenes derived from dimethylorsellinic acid (DMOA) and farnesyl pyrophosphate have attracted much biosynthetic attention, yet only recently have synthetic solutions to any family members appeared. A key point of divergence in DMOA-derived meroterpene biosynthesis is the protoaustinoid A carbocation, which can be diverted to either the berkeleyone, andrastin, or terretonin structural classes by cyclase-controlled rearrangement pathways. Shown herein is that the protoaustinoid bicyclo[3.3.1]nonane nucleus can be reverted to either andrastin or terretonin ring systems under abiotic reaction conditions. The first total syntheses of members of these natural product families are reported as their racemates.
二甲奥尔烯酸（DMOA）和法呢基焦磷酸衍生的倍半萜烯引起了人们对生物合成的极大关注，但直到最近才出现了针对任何家族成员的合成解决方案。DMOA 衍生的倍半萜烯生物合成中一个关键的分歧点是原阿替丁 A 碳正离子，它可以通过环化酶控制的重排途径转化为伯克利酮、阿替丁或特里顿宁结构类别。本文表明，在非生物反应条件下，原阿替丁双环[3.3.1]壬烷核可以重新转化为阿替丁或特里顿宁环系。这些天然产物家族成员的首次全合成作为外消旋体进行了报道。
