摘要
通过炔锂试剂11与环氮化合物10的区域和立体选择性加成构建了humantenine等钩吻生物碱不对称全合成路线中的重要中间体13;通过酸催化的烯醇-氧环合策略一步构建了humantenine等钩吻生物碱结构中的四氢吡喃环、环氧己烷、C7季碳中心和C3手性中心;最终从已知化合物7出发,以16步1.5%的总收率完成了humantenine(2),humantenine N4-oxide(3),gelseganines A(4)和gelseganines B(5)等钩吻生物碱关键中间体化合物6的不对称合成.
Humantenine-type compounds are a group of Gelsemium alkaloids isolated from Gelsemium elegans Benth that possess complex structures and remarkable activities. In this work, the synthetic approaches of them were investigated. The key structure of Gelsemium alkaloids humantenine （13） was efficiently constructed through a regionand stereoselectivity addition of compound 11 to compound 10. A multi-step, one pot enoloxonium cyclization cascade was used in a highly efficient way to construct, simultaneously, the tetrahydropyran ring, oxepane ring, C3 chiral carbon and C7 chiral quaternary carbon of humantenine （2）. Based the above created methodology, the key skeleton （6） of oxindole alkaloid humantenine （2）, humantenine N4-oxide （3）, gelseganines A（4）and gelseganines B （5） was asymmetric synthesized in 16 steps with a total yield of 1.5%. The structures of the compounds were confirmed by IR, 1H NMR, 13C NMR and high resolution mass spectrometer（HRMS）. Especially, we successfully synthesized hmantenine-type skeleton which indicates this method has a widely range of applications.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2012年第12期2676-2680,共5页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:21021001)资助
