摘 要 活性二苯乙烯低聚茋ε-Viniferin和Dehydro-δ-viniferin是白藜芦醇二聚体的代表 性化合物，它们具有 2,3-二芳基苯并二氢呋喃和 2,3-二芳基苯并呋喃的特征性结构。 ε-Viniferin 及 Dehydro-δ-viniferin 的前体 δ-Viniferin 主要分布于葡萄科、买麻藤科、 龙脑香科等科的多种植物中，具有显著的抗炎、抗菌、抗氧化等生物活性。由于结 构复杂，全合成困难，目前对该类化合物的全合成研究报道不多。 论文综述了金属参与的芳烃氢化研究进展，为芳香族化合物的氢化研究提供了 可参考的资料。 以3,5–二羟基苯甲酸和 3,5–二羟基苯乙酮为起始原料，通过14步反应，以6.81% 的总产率完成了活性天然产物 ε-Viniferin 的全合成研究，开发了一条实用的全合成 路线。合成中，探索了 C-4 位甲酯基取代的 2,3–二芳基苯并呋喃中间体脱除甲基保 护基的方法，实现了甲基保护基的完全脱除；首次实现了在不保护酚羟基的条件下， 以 TFA/TES 为催化剂还原较难还原的 2,3–二芳基苯并呋喃双键的反应；选择 MOM 保护 ε-Viniferin 结构中的多个酚羟基，首次实现了在不稳定的苯丙二氢呋喃环和苯 乙烯双键存在的条件下，高效脱除 ε-Viniferin 保护基的反应。合成研究为较难还原 的多酚类 2,3–二芳基苯并呋喃双键的还原，以及还原反应中羟基保护基的选择，提 供了有价值的参考，为活性 ε-Viniferin 及其衍生物的合成和构效关系研究提供了物 质基础。 在研究 Amberlyst 15 催化的 Dehydro-δ-viniferin 全合成的基础上，以金属-卤素 交换反应为关键反应，研究发展了一条简便实用的 Dehydro-δ-viniferin 的全合成路 线。以 3,5-二羟基苯乙酮和对羟基苯甲醛为起始原料，经 10 步反应，以 20.6%的产 率完成了 Dehydro-δ-viniferin 的全合成研究。以 i-PrMgCl∙LiCl 为催化剂，首次通过 金属-卤素交换实现了双碘代 α-芳氧基酮合成 3-芳基苯并二氢呋喃的反应。研究结 果为Dehydro-δ-viniferin及其相关衍生物的合成和构效关系研究，提供了物质基础。 发现并发展了一个在 PtCl2 催化下的实用、高效、条件温和的新型芳香族和酚类 化合物的转移氢化反应。机理研究认为，转移氢化是通过原位产生的过渡价态铂的 连续单电子转移 (SET)实现的，环己酮(Cy=O) 是酚类化合物氢化脱氧 (HDO) 反应 的关键中间体。研究结果显示，转移氢化可在 20°C 至 30°C 的温和条件下进行；伯 醇、仲醇和叔醇均可作为氢供体和反应溶剂，酸和水对反应进程没有明显影响。反 应中，单环芳烃、多环芳烃、杂环芳烃和稠环芳烃均具有较高的转化率。反应的发 现和研究为芳香类和酚类化合物的氢化和氢化脱氧反应提供了新的选择。

ABSTRACT Active stilbene oligomers ε-Viniferin and Dehydro-δ-viniferin, having 2,3-diaryl dihydrobenzofuran or 2,3-diarylbenzofuran characteristic structure, were representative natural products of resveratrol dimers. ε-Viniferin and δ-Viniferin, the precursor of Dehydro-δ-viniferin, distributed mainly in the families of Vitacae, Dipterocarpaceae, Gnetaceae and so on. As reported in the literature, they showed significant antiinflammatory, antibacterium, anti-oxidant and other biological activities. A few studies on their total syntheses have been reported up to now due to their complex structures. In this thesis, studies on the hydrogenation reaction of aromatic hydrocarbons involving metals were summarised and commenced, which provide valuable information for the investigation of the hydrogenation of aromatic hydrocarbons. With commercial 3,5-dihydroxybezoic acid and 3,5-dihydroxybenzophenone as starting materials, a facile and practical total synthesetic approach of naturally active εViniferin has been achieved in 14 steps and 6.81% overall yield. Demethylation of the intermediate 2,3-diarylbenzofuran with methoxycarbonyl substituted at C-4 has been achieved through the exploration of deprotection method. Using TFA/TES as catalyst, reduction of the double bond of 2,3-diarylbenzofuran in the presence of hydoxyls was accessed for the first time. Selecting MOM as phenolic hydroxyl protective group of εViniferin, Deprotection reaction was efficiently accomplished for the first time in the presence of unstable 2,3-diaryl dihydrobenzofuran ring and styryl double bond. The research results are helpful for the reduction of 2,3-diarylbenzofuran ring of polyphenols that is hard to be reduced and the selection of hydroxyl protective group in the reduction reaction. These results will also provide basis for the synthesis and investigation of structure-activity relationships of ε-Viniferin and its derivatives. On the basis of the total synthesis of Dehydro-δ-viniferin catalyzed by amberlyst 15, using metal-halogen exchange as key step, a versatile and practical total synthetic approach of Dehydro-δ-viniferin has been achieved in 10 steps and 20.6% overall yield with commercial 3,5-dihydroxybenzophenone and 4-hydroxybenzaldehyde as starting materials. Catalyzed by i-PrMgCl∙LiCl, the synthesis of 3-aryldihydrobenzofuran from αaryloxyketone diiodine through metal-halogen exchange was achieved for the first time. These results will provide basis for the synthesis and the investigation of structure-activityrelationships of Dehydro-δ-viniferin and its derivatives. Using PtCl2 as catalyst, a highly efficient transfer hydrogenation reaction of aromatics and phenolics under unprecedented, mild conditions was studied and developed. Mechanism investigation indicated that the reduction of aromatic ring was proceeded via successive single electron transfer (SET) mediated by in situ-generated transition-valent platinum. Cyclohexanone (Cy=O) was proven to be the key intermediate in the hydrodeoxygenation (HDO) process. PtCl2-mediated transfer hydrogenation reaction can be performed effectively at temperatures as low as 20 °C to 30 °C. Primary, secondary, and tertiary alcohols can serve as good H‒donors and solvents. Acids and water have no negative influence on the process. Monocyclic and polycyclic aromatic hydrocarbons, and fused-ring and heterocyclic aromatic hydrocarbons were successfully converted into cycloalkanes and alcohols with good to excellent yields . These findings offer novel process options for hydrogenation (HYD) and HDO of aromatic and phenolic compounds.