Department of Applied Chemistry, Faculty of Science , Tokyo University of Science , 1-3 Kagurazaka , Shinjuku-ku, Tokyo 162-8601 , Japan.
Department of Chemistry, Faculty of Science , Tokyo University of Science , 1-3 Kagurazaka , Shinjuku-ku, Tokyo 162-8601 , Japan.
J Nat Prod. 2018 Nov 26;81(11):2364-2370. doi: 10.1021/acs.jnatprod.8b00215. Epub 2018 Oct 30.
The first total synthesis of violaceoid A, a cytotoxic agent, and the asymmetric total synthesis of (-)- and (+)-violaceoid B are reported. The precursor was accessed by desymmetrization of a substituted quinol moiety, and the racemic secondary alcohol was kinetically resolved using a chiral nucleophilic catalyst. The asymmetric synthesis of (-)- and (+)-violaceoid B elucidated the absolute configuration of the naturally occurring violaceoid B. Synthetic violaceoid A inhibited the growth of human breast cancer cell lines MCF-7 and Hs 578T at concentrations of less than 100 μM, while ( S)- and ( R)-violaceoid B were inactive.
报道了细胞毒性剂紫罗烯 A 的首次全合成以及 (-)-和 (+)-紫罗烯 B 的不对称全合成。通过取代的喹啉部分的去对称化获得了前体，并且通过手性亲核催化剂动力学拆分了外消旋仲醇。 (-)-和 (+)-紫罗烯 B 的不对称合成阐明了天然存在的紫罗烯 B 的绝对构型。合成的紫罗烯 A 在低于 100 μM 的浓度下抑制人乳腺癌细胞系 MCF-7 和 Hs 578T 的生长，而 (S)-和 (R)-紫罗烯 B 则没有活性。
