Soldanelline B − The First Acylated Nonlinear Tetrasaccharide Macrolactone from the European ConvolvulaceaeCalystegia soldanella

Abstract

The first acylated nonlinear tetrasaccharide resin glycoside, soldanelline B (1), and its fatty acid derivative soldanellic acid B (2), have been isolated from a Portuguese Convolvula- [a] 369 ceae Calystegia soldanella. The structures were elucidated using high-field NMR spectroscopy, FAB mass spectrometry and chemical studies.

Calysolins I–IV, Resin Glycosides from Calystegia soldanella

“…Compound 5 was identified as soldanelline B on the basis of its physical and spectroscopic data. 4 The calysolins in this study have an intramolecular cyclic ester structure. Therefore, they can be classified as jalapin-type compounds.…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B by 1 H NMR spectroscopic comparison with that of an authentic sample . In the negative-ion FABMS, 1 exhibited a [M – H] − ion peak at m / z 1053 and fragment ion peaks at m / z 953 [1053 – 100 (niloyl unit (Nla))] − , 825 [1053 – 144 (hexosyl unit – H 2 O) – 84 (2-methylbutyryl unit (Mba))] − , 807 [953 – 146 (methylpentosyl unit)] − , 725 [825 – 100] − , 579 [725 −146] − , 417 [579 – 162] − , and 271 [417 – 146] − (Figure S22, Supporting Information).…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B 4 by 1 H NMR spectroscopic comparison with that of an authentic sample. 5 assignable to three carboxyl carbons (δ 175.4, 175.3, 172.9) and four anomeric carbons (δ 103.6, 101.7, 99.9, 98.1).…”

“…Therefore, the ester linkages of Nla, Jla, and Mba could be located at the OH-2 of Rha, the OH-2 of Glc′, and the OH-3 of Glc′, respectively. Taking the J values of signals due to the anomeric and methine protons of the sugar moiety into account, the conformations of the quinovopyranosyl and glucopyranosyl units were 4 C 1 and that of the rhamnopyranosyl unit was concluded to be 1 C 4 . The configurations of the component 2-methylbutyric acid and nilic acid units of the crude resin glycoside fraction of this plant have been determined previously as S and 2S,3S, respectively.…”

Calysolins I–IV, Resin Glycosides from Calystegia soldanella

“…Compound 5 was identified as soldanelline B on the basis of its physical and spectroscopic data. 4 The calysolins in this study have an intramolecular cyclic ester structure. Therefore, they can be classified as jalapin-type compounds.…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B by 1 H NMR spectroscopic comparison with that of an authentic sample . In the negative-ion FABMS, 1 exhibited a [M – H] − ion peak at m / z 1053 and fragment ion peaks at m / z 953 [1053 – 100 (niloyl unit (Nla))] − , 825 [1053 – 144 (hexosyl unit – H 2 O) – 84 (2-methylbutyryl unit (Mba))] − , 807 [953 – 146 (methylpentosyl unit)] − , 725 [825 – 100] − , 579 [725 −146] − , 417 [579 – 162] − , and 271 [417 – 146] − (Figure S22, Supporting Information).…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B 4 by 1 H NMR spectroscopic comparison with that of an authentic sample. 5 assignable to three carboxyl carbons (δ 175.4, 175.3, 172.9) and four anomeric carbons (δ 103.6, 101.7, 99.9, 98.1).…”

“…Therefore, the ester linkages of Nla, Jla, and Mba could be located at the OH-2 of Rha, the OH-2 of Glc′, and the OH-3 of Glc′, respectively. Taking the J values of signals due to the anomeric and methine protons of the sugar moiety into account, the conformations of the quinovopyranosyl and glucopyranosyl units were 4 C 1 and that of the rhamnopyranosyl unit was concluded to be 1 C 4 . The configurations of the component 2-methylbutyric acid and nilic acid units of the crude resin glycoside fraction of this plant have been determined previously as S and 2S,3S, respectively.…”

Chemistry and biological activity of resin glycosides from Convolvulaceae species

“…58 The carboxyl group of the aglycone moiety linked with the hydroxyl group of the Nla, making muricatin IX (34) the first representative of resin glycosides in which an organic acid connects the sugar moiety and the aglycone moiety to form macrocyclic ester ring. Moreover, four other resin glycosides derived from muricatic acid C, calonyctins F-H (35)(36)(37) and calonyctin J (38), were also identified from the seeds of I. muricata. 55 Calonyctins F-H (35)(36)(37) all had an Nla residue located at the C-2 position of the rhamnose unit, hydroxyl group of which was linked with the carboxyl group of the aglycone moiety to form a 25-membered ring.…”

Calysolins I–IV, Resin Glycosides from Calystegia soldanella

“…Compound 5 was identified as soldanelline B on the basis of its physical and spectroscopic data. 4 The calysolins in this study have an intramolecular cyclic ester structure. Therefore, they can be classified as jalapin-type compounds.…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B by 1 H NMR spectroscopic comparison with that of an authentic sample . In the negative-ion FABMS, 1 exhibited a [M – H] − ion peak at m / z 1053 and fragment ion peaks at m / z 953 [1053 – 100 (niloyl unit (Nla))] − , 825 [1053 – 144 (hexosyl unit – H 2 O) – 84 (2-methylbutyryl unit (Mba))] − , 807 [953 – 146 (methylpentosyl unit)] − , 725 [825 – 100] − , 579 [725 −146] − , 417 [579 – 162] − , and 271 [417 – 146] − (Figure S22, Supporting Information).…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B 4 by 1 H NMR spectroscopic comparison with that of an authentic sample. 5 assignable to three carboxyl carbons (δ 175.4, 175.3, 172.9) and four anomeric carbons (δ 103.6, 101.7, 99.9, 98.1).…”

“…Therefore, the ester linkages of Nla, Jla, and Mba could be located at the OH-2 of Rha, the OH-2 of Glc′, and the OH-3 of Glc′, respectively. Taking the J values of signals due to the anomeric and methine protons of the sugar moiety into account, the conformations of the quinovopyranosyl and glucopyranosyl units were 4 C 1 and that of the rhamnopyranosyl unit was concluded to be 1 C 4 . The configurations of the component 2-methylbutyric acid and nilic acid units of the crude resin glycoside fraction of this plant have been determined previously as S and 2S,3S, respectively.…”

Chemistry and biological activity of resin glycosides from Convolvulaceae species

“…58 The carboxyl group of the aglycone moiety linked with the hydroxyl group of the Nla, making muricatin IX (34) the first representative of resin glycosides in which an organic acid connects the sugar moiety and the aglycone moiety to form macrocyclic ester ring. Moreover, four other resin glycosides derived from muricatic acid C, calonyctins F-H (35)(36)(37) and calonyctin J (38), were also identified from the seeds of I. muricata. 55 Calonyctins F-H (35)(36)(37) all had an Nla residue located at the C-2 position of the rhamnose unit, hydroxyl group of which was linked with the carboxyl group of the aglycone moiety to form a 25-membered ring.…”

Calysolins I–IV, Resin Glycosides from Calystegia soldanella

“…Compound 5 was identified as soldanelline B on the basis of its physical and spectroscopic data. 4 The calysolins in this study have an intramolecular cyclic ester structure. Therefore, they can be classified as jalapin-type compounds.…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B by 1 H NMR spectroscopic comparison with that of an authentic sample . In the negative-ion FABMS, 1 exhibited a [M – H] − ion peak at m / z 1053 and fragment ion peaks at m / z 953 [1053 – 100 (niloyl unit (Nla))] − , 825 [1053 – 144 (hexosyl unit – H 2 O) – 84 (2-methylbutyryl unit (Mba))] − , 807 [953 – 146 (methylpentosyl unit)] − , 725 [825 – 100] − , 579 [725 −146] − , 417 [579 – 162] − , and 271 [417 – 146] − (Figure S22, Supporting Information).…”

“…GC of the organic acid fraction revealed the presence of 2-methylbutyric acid and nilic acid. The later was identified in soldanellic acid B 4 by 1 H NMR spectroscopic comparison with that of an authentic sample. 5 assignable to three carboxyl carbons (δ 175.4, 175.3, 172.9) and four anomeric carbons (δ 103.6, 101.7, 99.9, 98.1).…”

“…Therefore, the ester linkages of Nla, Jla, and Mba could be located at the OH-2 of Rha, the OH-2 of Glc′, and the OH-3 of Glc′, respectively. Taking the J values of signals due to the anomeric and methine protons of the sugar moiety into account, the conformations of the quinovopyranosyl and glucopyranosyl units were 4 C 1 and that of the rhamnopyranosyl unit was concluded to be 1 C 4 . The configurations of the component 2-methylbutyric acid and nilic acid units of the crude resin glycoside fraction of this plant have been determined previously as S and 2S,3S, respectively.…”

Chemistry and biological activity of resin glycosides from Convolvulaceae species

“…58 The carboxyl group of the aglycone moiety linked with the hydroxyl group of the Nla, making muricatin IX (34) the first representative of resin glycosides in which an organic acid connects the sugar moiety and the aglycone moiety to form macrocyclic ester ring. Moreover, four other resin glycosides derived from muricatic acid C, calonyctins F-H (35)(36)(37) and calonyctin J (38), were also identified from the seeds of I. muricata. 55 Calonyctins F-H (35)(36)(37) all had an Nla residue located at the C-2 position of the rhamnose unit, hydroxyl group of which was linked with the carboxyl group of the aglycone moiety to form a 25-membered ring.…”