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

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