Key Laboratory of Structure-Based Drug Design and Discovery (Shenyang Pharmaceutical University), Ministry of Education , Shenyang 110016, P. R. China.
Institute of Drug Research in Medicine Capital of China , Benxi 117000, P. R. China.
J Org Chem. 2017 Oct 20;82(20):11102-11109. doi: 10.1021/acs.joc.7b02066. Epub 2017 Oct 2.
A cascade [3,3]-sigmatropic rearrangement/aromatization strategy to the synthesis of 2-(3-methylbenzofuran-2-yl)phenol derivatives was developed and applied to the collective syntheses of seven 2-arylbenzofuran-containing natural products, namely glycybenzofuran, glycyuralin E, lespedezol A, puerariafuran, 7,2',4'-trihydroxy-3-benzofurancarboxylic acid, coumestrol, and 4'-O-methylcoumestrol. Among them, the total syntheses of glycybenzofuran, glycyuralin E, puerariafuran, 7,2',4'-trihydroxy-3-benzofurancarboxylic acid, and 4'-O-methylcoumestrol were reported for the first time. The practicality of this novel strategy in preparation of the key intermediates was demonstrated by performing the reaction on gram scale and by synthesizing a series of natural products with 2-(3-methylbenzofuran-2-yl)phenol scaffolds in a common strategy.
发展了一种级联[3,3]-σ重排/芳构化策略，用于合成 2-(3-甲基苯并呋喃-2-基)苯酚衍生物，并将其应用于七种含有 2-芳基苯并呋喃的天然产物的集体合成，即甘氨苯并呋喃、甘氨尿嘧啶 E、莱苏多醇 A、葛根素、7,2',4'-三羟基-3-苯并呋喃羧酸、大豆素和 4'-O-甲基大豆素。其中，甘氨苯并呋喃、甘氨尿嘧啶 E、葛根素、7,2',4'-三羟基-3-苯并呋喃羧酸和 4'-O-甲基大豆素的全合成首次被报道。该新策略在关键中间体制备中的实用性通过克级规模的反应以及通过共同策略合成一系列具有 2-(3-甲基苯并呋喃-2-基)苯酚支架的天然产物得到证明。
