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引用次数: 0
摘要
这项研究展示了以区域特异性方式将乙烯基酯直接转化为选择性保护的 6-酰基间苯二酚(4-烷氧基/芳氧基-2-羟基芳基酮)。间苯二酚酮类化合物是首次合成,与其传统的来源不同,它们源自非苯类池材料。由于中间产物的稳定性和反应性问题,将环己烯酮转化为苯酚或间苯二酚基芳基酮仍然具有挑战性。针对这一关键问题,我们引入了一种新策略:乙烯基酯的单锅顺序酰化和氧化芳香化。这种创新方法旨在克服长期存在的障碍,促进各种间苯二酚酮的合成。此外,这种方法对于合成功能化二芳基醚以及生物活性天然产品和药物分子(如血管紧张素、异桔梗素、去甲山梨醇、庞加诺酮 VII 和异丙黄酮)的全合成也很有价值。通过在合成后期引入间苯二酚官能团,它还可用于修饰生物活性酸和醇。羟苯甲酯的合成类似物具有优异的紫外线(UV)吸收特性,可有效覆盖整个紫外线-A 和紫外线-B 区域,波长范围从 230 纳米到 410 纳米。
Tandem Acylation and Aromatization of Vinylogous Esters: A Regiospecific Approach to Resorcinyl Ketones
This study demonstrates the direct conversion of vinylogous esters into selectively protected 6-acyl resorcinols (4-alkoxy/aryloxy-2-hydroxy arylketones) in a regiospecific manner. Resorcinyl ketones are first-time synthesized, diverging from their traditional roots, originating from non-benzenoid pool materials. Converting cyclohexenones into phenol- or resorcinol-based arylketones remains challenging due to the stability and reactivity issues of intermediate products. Addressing this critical gap, we introduce a novel strategy: sequential one-pot acylation and oxidative aromatization of vinylogous esters. This innovative approach aims to surmount the long-standing barrier, facilitating the synthesis of diverse resorcinyl ketones. Furthermore, this method proves valuable for the synthesis of functionalized diaryl ethers and in the total synthesis of bioactive natural products and drug molecules such as angolensin, isoliquiritigenin, demethylsorbicillin, ponganone VII, and ipriflavone. It is also useful for modifying bioactive acids and alcohols by introducing a resorcinol functionality in the late stage of synthesis. Synthetic analogues of oxybenzone demonstrated superior ultraviolet (UV) absorption properties, effectively covering the entire UV-A and UV-B regions, spanning from 230 to 410 nm.
期刊介绍:
The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.