Total Synthesis of (−)-Antroalbocin A Enabled by a Strain Release-Controlled Photochemical 1,3-Acyl Shift,Organic Letters

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Total Synthesis of (−)-Antroalbocin A Enabled by a Strain Release-Controlled Photochemical 1,3-Acyl Shift
Organic Letters ( IF 4.9 ) Pub Date : 2022-08-01 , DOI: 10.1021/acs.orglett.2c02347
Björn Siekmeyer ₁ , Dennis Lübken ₁ , Kevin Bajerke ₁ , Bastian Bernhardt ₂ , Peter R Schreiner ₂ , Markus Kalesse _{1,

3,

4}

Affiliation

The first bioinspired, enantioselective, and protecting group free total synthesis of the antibacterial sesquiterpenoid (−)-antroalbocin A (1) has been achieved in 12 steps (5.4% overall yield) from dimedone. An organocatalytic Robinson annulation gave rapid access to the tricyclic enone (19) 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 8. The transformation of 8 to its bridged isomer 5 is exergonic and, therefore, enables an increased conversion compared to unstrained substrates.

中文翻译：

由应变释放控制的光化学 1,3-酰基转移实现 (-)-Antroalbocin A 的全合成

抗菌倍半萜类化合物 (-)-antroalbocin A ( 1 ) 的第一个生物启发、对映选择性和无保护基团的全合成已经从二甲酮通过 12 个步骤（总产率 5.4%）实现。有机催化的 Robinson 环化可以快速获得三环烯酮 ( 19 ) 作为去共轭和 sigmatropic 1,3-酰基转移的光化学多米诺过程的起始材料。该过程的计算数据表明，1,3-酰基转移受益于高度应变的 1,3-烯酮8。8向其桥接异构体5的转变是放能的，因此与未应变的底物相比，能够提高转化率。

更新日期：2022-08-01

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