有机化学 ›› 2020, Vol. 40 ›› Issue (10): 3420-3425.DOI: 10.6023/cjoc202005058 上一篇    下一篇

研究论文

15-Oxopuupehenoic Acid可能结构1b的不对称全合成

宋华月, 刘霖, 谢新刚   

  1. 兰州大学化学化工学院 功能有机分子化学国家重点实验室 兰州 730000
  • 收稿日期:2020-05-22 修回日期:2020-05-29 发布日期:2020-06-10
  • 通讯作者: 谢新刚 E-mail:xiexg@lzu.edu.cn
  • 基金资助:
    国家自然科学基金(No.21472079)资助项目.

Asymmetric Total Synthesis of the Possible Structure 1b of 15-Oxopuupehenoic Acid

Song Huayue, Liu Lin, Xie Xingang   

  1. State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000
  • Received:2020-05-22 Revised:2020-05-29 Published:2020-06-10
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 21472079).

15-Oxopuupehenoic acid是Crews小组2009年从巴布新几内亚的特种海绵中分离得到的一个新杂倍半萜.分离作者由波谱数据分析其可能骨架结构为四环色满酮1a1b或苯并2-氧杂-环庚酮1c1d,进而通过二维gHMBC相关核磁谱图分析判定其结构为1a.然而,近期Alvarez-Manzaneda和Chahboun小组通过化学合成得到的化合物1a的波谱数据却无法与天然产物相吻合.我们以R-(-)-香芹酮为起始原料,通过偶联-环化的汇聚式合成策略,以Suzuki羰化偶联反应和KOH促进的分子内环化反应为关键反应,构建了15-Oxopuupehenoic acid独特的苯并-γ-吡喃酮骨架,完成了其可能结构1b的不对称全合成.化合物1b的谱图数据和天然产物亦不相符,因此天然15-oxopuupehenoic acid的结构需要进一步修正.

关键词: 15-oxopuupehenoic acid, Suzuki羰化偶联, KOH促进, 分子内环化反应, 色满酮

15-Oxopuupehenoic acid is a new merosesquiterpenoid isolated in 2009 by Crews group from the crude sponge extracts prioritized a Papua New Guinea collection of Hyrtios sp. Its possible structure was deduced to be tetracyclic chromanones 1a~1b or benzo[c]oxepin-1(3H)-ones 1c~1d based on the spectra data, and later determinded to be 1a by analysis of its gHMBC correlations spectra. Recently Alvarez-Manzaneda and Chahboun group obtained 1a by chemical synthesis which spectra data did not match well with those of natural 15-oxopuupehenoic acid. We started from R-(-)-carvone and approched its possible structure 1b through a convergent coupling-cyclization strategy. Our sythesis featured Suzuki carbonylative coupling reaction and KOH promoted intramolecular cyclization reaction to construct the unique chromanone subunit. The spectra data of synthetic 1b did not match well with those of natural 15-oxopuupehenoic acid either which indicated its structure needed revision.

Key words: 15-oxopuupehenoic acid, Suzuki carbonylative coupling, KOH promotion, intramolecular cyclization, chromanone