C14-Polyacetylene glucosides from Codonopsis pilosula

Seven new C-14-polyacetylene glucosides codonopilodiynosides A-G (1-7) were isolated from an aqueous extract of the Codonopsis pilosula roots. Their structures were determined by spectroscopic and chemical methods as (-)-(5S,6E,12E)-tetradeca-6,12-dien-8,10-diyn-1,5,14-triol 5-O-beta-D-glucopyranoside (1), (-)-(5S,6E,12E)-tetradeca-6,12-dien-8,10-diyn-1,5,14-triol 5-O-beta-D-glucopyranosyl-(1 ''-> 2')-beta-D-glucopyranoside (2), (-)-(5S,6E,12E)-tetradeca-6,12-dien- 8,10-diyn-1,5,14-triol 5,14-di-O-beta-D-glucopyranoside (3), (-)-(5S,6E)-tetradeca-6-en-8,10-diyn-1,5,14-triol 5-O-beta-D- glucopyranoside (4), (-)-(5S,6E,12E)-tetradeca-6,12-dien-8,10-diyn-1,5-14-triol 5-O-beta-D-glucopyranosyl-(1 ''-> 2')-beta-D-glucopyranoside (5), (-)-(6S,4E,12E)-tetradeca-6,12-dien-8,10-diyn-1,6-diol 6-O-beta-D-glucopyranosyl-(1 ''-> 2')-beta-D-glucopyranoside (6), and (-)-(5S,6E)-tetradeca-6-en-1,5-epoxy-8,10-diyn-14-ol 14-O-beta-D-glucopyranosyl-(1 ''-> 2')-beta-D-glucopyranoside (7), respectively. The absolute configurations of 1-7 were assigned by enzymatic hydrolysis followed by isolation of glucose and aglycones (1a and 4a-7a), and subsequent comparison of specific rotation, TLC, and H-1 NMR data of the glucose with an authentic sugar sample and application of modified Mosher's method based on the MPA determination rule of Delta delta(RS) values for 1a and 4a, and (S) values for 6a. The configuration of 7 was assigned by electronic circular dichroism calculations based on the quantum-mechanical time-dependent density functional theory.