Siekmeyer Björn, Lübken Dennis, Bajerke Kevin, Bernhardt Bastian, Schreiner Peter R, Kalesse Markus
Institute of Organic Chemistry, Gottfried Wilhelm Leibniz University Hannover, 30167Hannover, Germany.
Institute of Organic Chemistry, Justus Liebig University, 35392Giessen, Germany.
Org Lett. 2022 Aug 12;24(31):5812-5816. doi: 10.1021/acs.orglett.2c02347. Epub 2022 Aug 1.
The first bioinspired, enantioselective, and protecting group free total synthesis of the antibacterial sesquiterpenoid (-)-antroalbocin A () has been achieved in 12 steps (5.4% overall yield) from dimedone. An organocatalytic Robinson annulation gave rapid access to the tricyclic enone () as starting material for the photochemical domino process of deconjugation and sigmatropic 1,3-acyl shift. Computational data of this process indicate that the 1,3-acyl shift benefits from the highly strained 1,3-enone . The transformation of to its bridged isomer is exergonic and, therefore, enables an increased conversion compared to unstrained substrates.
已从环已二酮出发，通过12步反应（总产率5.4%）首次实现了对具有抗菌活性的倍半萜（-）-antroalbocin A（）的仿生、对映选择性且无保护基的全合成。有机催化的罗宾逊缩环反应能够快速得到三环烯酮（），作为光化学多米诺反应中去共轭和1,3-酰基迁移反应的起始原料。该过程的计算数据表明，1,3-酰基迁移反应得益于高度张力的1,3-烯酮。将转化为其桥环异构体是放能的，因此与无张力的底物相比，能提高转化率。
