(±)-Walskiiglucinol A, a pair of rearranged acylphloroglucinol derivative enantiomers from Hypericum przewalskii. Issue 24 (8th June 2022)

• Record Type: Journal Article
• Authors: Duan, Yulin; Bu, Pengfei; Guo, Yi; Shi, Zhengyi; Cao, Yunfang; Zhang, Yeting; Hu, Hong; Hu, Hankun; Qi, Changxing; Zhang, Yonghui
• Is Part Of: Organic & biomolecular chemistry. Volume 20:Issue 24(2022)
• Page Start: 4970
• Page End: 4975
• Publication Date: 2022-06-08
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/d2ob00562j
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : A pair of rearranged acylphloroglucinol derivative enantiomers with a 1-oxaspiro[4.4]nonane skeleton, derived from monocyclic polyprenylated acylphloroglucinols (MPAPs), was obtained from Hypericum przewalskii . Abstract : (±)-Walskiiglucinol A (1a/1b ), a pair of rearranged acylphloroglucinol derivatives with a new carbon skeleton, was obtained from Hypericum przewalskii . Compounds 1a/1b were the first examples of naturally occurring acylphloroglucinol derivatives possessing a unique 1-oxaspiro[4.4]nonane core bearing a new 5/5 ring system. Their planar and relative structures were identified by extensive spectroscopic analysis and NMR chemical shift calculations with DP4+ probability analysis, and their absolute configurations were determined by electronic circular dichroism (ECD) calculations. A plausible biogenetic pathway of 1a/1b was proposed in which the breakage of the C-2/C-3 linkage via a retro-Claisen reaction and the cyclization between C-3 and C-1 were proposed as key steps. The isolates were evaluated for cytotoxic activities against a panel of cancer cell lines and anti-inflammatory activities against lipopolysaccharide (LPS)-induced NO production, and compounds 1a/1b showed moderate cytotoxic activities with IC50 values ranging from 9.72 to 36.75 μM.