Hyperforones A–C, benzoyl-migrated [5.3.1]-type polycyclic polyprenylated acylphloroglucinols from Hypericum forrestii,Organic Chemistry Frontiers

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Hyperforones A–C, benzoyl-migrated [5.3.1]-type polycyclic polyprenylated acylphloroglucinols from Hypericum forrestii
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2020-03-03 , DOI: 10.1039/d0qo00152j
Wei-Jia Lu _{1,

2,

3,

4,

5} , Wen-Jun Xu _{1,

2,

3,

4,

5} , Yan-Qiu Zhang _{1,

2,

3,

4,

5} , Yi-Ran Li _{1,

2,

3,

4,

5} , Xin Zhou _{1,

2,

3,

4,

5} , Qi-Ji Li _{1,

2,

3,

4,

5} , Hao Zhang _{1,

2,

3,

4,

5} , Jun Luo _{1,

2,

3,

4,

5} , Ling-Yi Kong _{1,

2,

3,

4,

5}

Affiliation

Three unprecedented benzoyl-migrated polycyclic polyprenylated acylphloroglucinols (PPAPs), hyperforones A–C (1–3), were isolated from Hypericum forrestii, together with a new benzoyl-substituted analogue (4) of hyperforin. Compounds 1–3 are the first examples of naturally occurring benzoyl-PPAPs with a unique C-1 H-substituted bicyclo[5.3.1]hendecane scaffold. Their structures and absolute configurations were established by HRESIMS, NMR spectroscopy data, electronic circular dichroism (ECD) exciton chirality method, ECD calculations, and gauge-independent atomic orbital (GIAO) NMR calculations with DP4+ analyses. A plausible biosynthetic formation of the benzoyl-migrated C-1 H-substituted bicyclo[5.3.1]hendecane skeleton in 1–3via a sterically favored hemiketalization/Retro-Claisen cascade was proposed. Bzhyperforin (4) showed significant cytotoxicity against MDA-MB-231 cells with an IC₅₀ value of 6.88 ± 1.37 μM.

中文翻译：

Hyperforones A–C，苯甲酸迁移的[5.3.1]型多环多烯丙基化酰基间苯三酚

从金丝桃属植物金丝桃中分离出了三种前所未有的苯甲酰迁移的多环多烯丙基化酰基间苯三酚（PPAPs），即Hyperforones A–C（1-3），以及新的hyperforin苯甲酰取代的类似物（4）。化合物1-3是具有独特的C-1 H取代的双环[5.3.1]十一烷骨架的天然存在的苯甲酰基-PPAP的第一个实例。通过HRESIMS，NMR光谱数据，电子圆二色性（ECD）激子手性方法，ECD计算以及DP4 +分析，与轨距无关的原子轨道（GIAO）NMR计算确定了它们的结构和绝对构型。苯甲酰基迁移的C-1 H取代的双环[5.3.1]十一烷骨架的可能的生物合成形式提出了通过空间偏爱的半缩合/ Retro-Claisen级联进行的1-3。Bzhyperforin（4）对MDA-MB-231细胞表现出明显的细胞毒性，IC ₅₀值为6.88±1.37μM。

更新日期：2020-03-03

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