摘要/Abstract
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1a～1b或苯并2-氧杂-环庚酮1c～1d，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
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