AbstractThe 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.