New Acylated Saponins from Polygala myrtifolia

The ten new acylated presenegenin (=(2β,3β,4α)‐2,3,27‐trihydroxyolean‐12‐ene‐23,28‐dioic acid) glycosides 1 – 10 have been isolated by successive MPLC from the roots of Polygala myrtifolia L. as five inseparable mixtures of the trans‐ and cis‐4‐methoxycinnamoyl derivatives, i.e., myrtifoliosides A₁/A₂ ( 1 / 2 ), B₁/B₂ ( 3 / 4 ), C₁/C₂ ( 5 / 6 ), D₁/D₂ ( 7 / 8 ), and E₁/E₂ ( 9 / 10 ). Their structures were elucidated mainly by extensive spectroscopic experiments, including 2D NMR techniques, as 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐galactopyranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐[D ‐apio‐β‐D ‐furanosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[α‐L ‐arabinopyranosyl‐(1→3)]‐4‐O‐(trans‐4‐methoxycinnamoyl)‐β‐D ‐fucopyranosyl} ester ( 1 ) and its cis‐isomer 2 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐galactopyranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐[D ‐apio‐β‐D ‐furanosyl‐(1→3)]‐α‐L ‐rhamnopyranosyl‐(1→2)‐4‐O‐(trans‐4‐methoxycinnamoyl)‐β‐D ‐fucopyranosyl} ester ( 3 ) and its cis‐isomer 4 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐galactopyranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐4‐O‐(trans‐4‐methoxycinnamoyl)‐β‐D ‐fucopyranosyl} ester ( 5 ) and its cis‐isomer 6 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐D ‐apio‐β‐D ‐furanosyl‐(1→3)‐O‐[β‐D ‐xylopyranosyl‐(1→4)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐4‐O‐(trans‐4‐methoxycinnamoyl)‐β‐D ‐fucopyranosyl} ester ( 7 ) and its cis‐isomer 8 , and 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐α‐L ‐arabinopyranosyl‐(1→3)‐O‐[β‐D ‐xylopyranosyl‐(1→4)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐4‐O‐(trans‐4‐ methoxycinnamoyl)‐β‐D ‐fucopyranosyl} ester ( 9 ) and its cis‐isomer 10 .