Feldman K S, Lawlor M D, Sahasrabudhe K
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA.
J Org Chem. 2000 Nov 17;65(23):8011-9. doi: 10.1021/jo0010936.
The total synthesis of the dimeric ellagitannin coriariin A is reported. The key reaction to access the dimeric framework was realized early in the synthesis pathway via a bis acylation reaction of a dehydrodigalloyl diacid with 2 equiv of a glucopyranose trichloroacetimidate. The glucose rings were subsequently functionalized, culminating in a double oxidative cyclization to form stereoselectively both (S)-HHDP ester units. This bis acylation strategy was also employed to prepare a gallotannin analogue of coriariin A whose earlier synthesis by orthoquinone dimerization was plagued by yield-limiting side reactions.
报道了二聚体鞣花单宁科瑞阿林A的全合成。在合成途径早期，通过脱氢双没食子酰二酸与2当量的吡喃葡萄糖三氯乙酰亚胺酯的双酰化反应，实现了构建二聚体骨架的关键反应。随后对葡萄糖环进行官能化，最终通过双重氧化环化反应立体选择性地形成两个(S)-六羟基联苯二甲酰酯单元。这种双酰化策略也被用于制备科瑞阿林A的没食子单宁类似物，其早期通过邻醌二聚化合成时受到产率限制的副反应困扰。
