摘要/Abstract

研究了白藜芦醇二聚体quadrangularin A（3）和pallidol（4）的全合成新方法学，设计了以廉价易得的3，5-二甲氧基苯乙腈（5）和3，5-二甲氧基苯甲醛（6）为原料，经9步反应得到天然产物quadrangularin A（3），总收率为2.6%；经11步反应得到天然产物pallidol（4），总收率为1.3%.其中，利用Knoevenagel反应在室温无需无水无氧条件下，简单高效地引入A、B两个对称或非对称芳环，拓展了二苯乙烯基多样性骨架结构中间体7，产率达98%以上，改善了文献报道中非对称结构拓展受限，产率低，操作复杂等问题.此外，通过巧妙构建4-烯醛骨架结构的关键中间体9，可高效地构筑C、D芳环，为拓展A、B、C和D芳环多样性结构的白藜芦醇类二聚体提供了新思路.所合成的中间体及天然产物结构均经¹H NMR，¹³C NMR，HRMS表征确证.
关键词: 白藜芦醇二聚体, 傅克反应, 格氏试剂加成, 全合成
This paper has focused on developing a novel methodology for the total synthesis of quadrangularin A (3) and pallidol (4). These two resveratrol dimers have been obtained from the inexpensive materials of 3,5-dimethoxybenzaldehyde (5) and 3,5-dimethoxybenzaldehyde (6) within 9 steps and 11 steps with total yields of 2.6% and 1.3%, respectively. The stilbene skeleton constructed by two symmetric or asymmetric aromatic rings (A and B) has been synthesized simply through Knoevenagel reaction under mild conditions with yield of more than 98%, which expanded the diversity of stilbene skeleton (7), and addressed the problems of limited expansion of asymmetric structure, low yield and complex operation. In addition, the key intermediate of 4-enaldehyde skeleton structure (9) could be used to construct aromatic rings of C and D efficiently, which has thrown light on the expansion of resveratrol dimers with aromatic ring A, B, C and D in diversity structure. All the intermediates and natural products have been characterized by ¹H NMR, ¹³C NMR, and HRMS.
Key words: resveratrol oligomer, Friedel-Crafts reaction, Grignard regent addition reaction, total synthesis


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