Instituto de Investigaciones Químico Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, Morelia, Michoacán 58030, Mexico.
Departamento de Química, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, Apartado 14-740, Mexico City 07000, Mexico.
J Nat Prod. 2021 Apr 23;84(4):1087-1095. doi: 10.1021/acs.jnatprod.0c01160. Epub 2021 Mar 18.
The partial or total hydrolysis of (3,4,5,6,9,10,11)-9,13-diangeloyloxylongipinan-1-one (), isolated from the roots of , gave alcohols or , respectively, which were subjected to molecular rearrangements with boron trifluoride etherate. Compound afforded (3,4,5,6,9,10,11)-11,13-oxyneomorelian-1-one () and (4,5,6,8,10)-10,13-oxyneojiquilp-2-en-1-one (), both possessing novel sesquiterpenoid skeletons. In turn, provided (3,4,5,6,9,11)-13-hydroxymoreli-10(14)-en-1-one () and . Acetylation of gave , thus allowing reduction of the C-1 carbonyl group to yield , which was rearranged to (1,3,4,5,6,9,10,11)-13-acetoxy-9,11-epoxyjiquilpane (), while an attempt to mesylate directly gave rearranged (3,4,5,6,9,11)-13-mesyloxymoreli-10(14)-en-1-one () through expulsion of the C-9 mesylate group by the antiperiplanar C-4-C-10 bond migration to C-4-C-9. In addition, treatment of with boron trifluoride etherate generated (3,4,5,6,9,11)-13-angeloyloxymoreli-10(14)-en-1-one (). The structures of - were elucidated by 1D and 2D NMR experiments and those of , , , , and were confirmed by single-crystal X-ray diffraction analysis.
从 的根部分离得到 (3,4,5,6,9,10,11)-9,13-二当归酰氧基长叶扁柏酮 ()，部分或完全水解后分别得到醇 或 ，它们分别用三氟化硼乙醚进行分子重排。化合物 生成 (3,4,5,6,9,10,11)-11,13-氧新莫雷利酮-1-酮 () 和 (4,5,6,8,10)-10,13-氧新吉奎尔-2-烯-1-酮 ()，这两种化合物均具有新型倍半萜骨架。反过来， 生成 (3,4,5,6,9,11)-13-羟莫雷利-10(14)-烯-1-酮 ()和 。 将 乙酰化得到 ，从而可以还原 C-1 羰基得到 ，该化合物发生重排生成 (1,3,4,5,6,9,10,11)-13-乙酰氧基-9,11-环氧吉奎尔烷 ()，而试图直接对 进行甲磺酰化，由于反式平面的 C-4-C-10 键迁移到 C-4-C-9，通过 C-9 甲磺酰基的逐出，直接得到重排的 (3,4,5,6,9,11)-13-甲磺酰氧基莫雷利-10(14)-烯-1-酮 ()。此外，用三氟化硼乙醚处理 生成 (3,4,5,6,9,11)-13-当归酰氧基莫雷利-10(14)-烯-1-酮 ()。 通过 1D 和 2D NMR 实验阐明了 -的结构，通过单晶 X 射线衍射分析证实了 、 、 、 、和 的结构。
