Structure, property, biogenesis, and activity of diterpenoid alkaloids containing a sulfonic acid group from Aconitum carmichaelii  

作　　者：Qinglan Guoy Huan Xiay Yuzhuo Wu Shuai Shao Chengbo Xu Tiantai Zhang Jiangong Shi 

机构地区：[1]State Key Laboratory of Bioactive Substance and Function of Natural Medicines,Institute of Materia Medica,Chinese Academy of Medical Sciences and Peking Union Medical College,Beijing 100050,China

出　　处：《Acta Pharmaceutica Sinica B》2020年第10期1954-1965,共12页药学学报（英文版）

基　　金：Financial support of the National Natural Sciences Foundation of China(81630094,21732008,and 81730093);CAMS Innovation Fund for Medical Science of China(2017-I2M-3-010 and 2016I2M-1-010);the Drug Innovation Major Project(2018ZX09711001-001-001,2018ZX09711001-001-003,and 2018ZX09711001-003-001,China)

摘　　要：Three new C20-diterpenoid alkaloids with a sulfonic acid unit,named aconicarmisulfonines B and C(1 and 2)and chuanfusulfonine A(3),respectively,were isolated from the Aconitum carmichaelii lateral roots("fu zi"in Chinese).Structures of 1-3 were determined by spectroscopic data analysis.Intriguing chemical properties and reactions were observed for the C20-diterpenoid alkaloids:(a)specific selective nucleophilic addition of the carbonyl(C-12)in 1 with CD3 OD;(b)interconversion between 1 and 2 in D2 O;(c)stereo-and/or regioselective deuterations of H-11αin 1-3 and both H-11αand H-11βin aconicarmisulfonine A(4);(d)TMSP-2,2,3,3-d4 promoted cleavage of the C-12-C-13 bond of 4 in D2 O;(e)dehydrogenation of 4 in pyridine-d5,and(f)Na2 SO3-assisted dehydrogenation and N-deethylation of songorine(5,a putative precursor of 1-4).Biogenetically,1 and 2 are correlated with 4,for which the same novel carbon skeleton is proposed to be derived from semipinacol rearrangements via migrations of C-13-C-16 and C-15-C-16 bonds of the napelline-type skeleton,respectively.Meanwhile,3 is a highly possible precursor or a concurrent product in the biosynthetic pathways of 1,2,and 4.In the acetic acid-induced mice writhing assay,at 1.0 mg/kg(i.p.),compounds 1,2,5,5 a,and 5 b exhibited analgesic effects against mice writhing.

关 键 词：RANUNCULACEAE Aconitum carmichaelii Sulfonated C20-diterpenoid alkaloid Aconicarmisulfonines Chuanfusulfonine A Analgesic effect 

分 类 号：R914[医药卫生—药物化学]