{"title":"20S-Protopanaxadiol 和 Betulafolientriol 的 12α-Epimers 的 β-D-Glucopyranosides 的合成","authors":"L. N. Atopkina, A. I. Kalinovsky","doi":"10.1007/s10600-024-04464-7","DOIUrl":null,"url":null,"abstract":"<p><i>β</i>-D-Glucopyranosides of 3<i>β</i>, 12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>1</b>) and 3<i>α</i>,12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>2</b>), close structural analogs of ginsenoside-Rh2 and a metabolite of <i>Panax ginseng</i> glycosides (compound K), were synthesized. Glycosylation of 20<i>S</i>-hydroxydammar-24-ene-3,12-dione (<b>5</b>) and 3<i>α</i>-acetoxy-20<i>S</i>-hydroxydammar-24-en-12-one (<b>6</b>) by 2,3,4,6-tetra-<i>O</i>-acetyl-<i>α</i>-D-glucopyranosyl bromide (<b>8</b>) under classical Koenig-Knorr reaction conditions followed by deacetylation by NaOMe in MeOH gave free 20-<i>O</i>-<i>β</i>-D-glucopyranosides <b>10</b> and <b>13</b>, treatment of which with NaBH<sub>4</sub> in i-PrOH formed 20-<i>O</i>-<i>β</i>-D- glucopyranosides of the 12<i>α</i>-epimers of 20S-protopanaxadiol <b>11</b> and betulafolientriol <b>14</b>. Condensation of 3<i>β</i>,12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>1</b>) and glycosyl donor <b>8</b> in the presence of Ag<sub>2</sub>O in CH<sub>2</sub>Cl<sub>2</sub> followed by removal of the protecting groups gave 3-<i>O</i>-<i>β</i>-D-glucopyranoside <b>16</b>; of 3<i>α</i>,12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>2</b>) under the same conditions, a mixture of 3- and 12-<i>O</i>-<i>β</i>-D-glucopyranosides <b>19</b> and <b>20</b>.</p>","PeriodicalId":514,"journal":{"name":"Chemistry of Natural Compounds","volume":null,"pages":null},"PeriodicalIF":0.8000,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis of β-D-Glucopyranosides of 12α-Epimers of 20S-Protopanaxadiol and Betulafolientriol\",\"authors\":\"L. N. Atopkina, A. I. Kalinovsky\",\"doi\":\"10.1007/s10600-024-04464-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><i>β</i>-D-Glucopyranosides of 3<i>β</i>, 12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>1</b>) and 3<i>α</i>,12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>2</b>), close structural analogs of ginsenoside-Rh2 and a metabolite of <i>Panax ginseng</i> glycosides (compound K), were synthesized. Glycosylation of 20<i>S</i>-hydroxydammar-24-ene-3,12-dione (<b>5</b>) and 3<i>α</i>-acetoxy-20<i>S</i>-hydroxydammar-24-en-12-one (<b>6</b>) by 2,3,4,6-tetra-<i>O</i>-acetyl-<i>α</i>-D-glucopyranosyl bromide (<b>8</b>) under classical Koenig-Knorr reaction conditions followed by deacetylation by NaOMe in MeOH gave free 20-<i>O</i>-<i>β</i>-D-glucopyranosides <b>10</b> and <b>13</b>, treatment of which with NaBH<sub>4</sub> in i-PrOH formed 20-<i>O</i>-<i>β</i>-D- glucopyranosides of the 12<i>α</i>-epimers of 20S-protopanaxadiol <b>11</b> and betulafolientriol <b>14</b>. Condensation of 3<i>β</i>,12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>1</b>) and glycosyl donor <b>8</b> in the presence of Ag<sub>2</sub>O in CH<sub>2</sub>Cl<sub>2</sub> followed by removal of the protecting groups gave 3-<i>O</i>-<i>β</i>-D-glucopyranoside <b>16</b>; of 3<i>α</i>,12<i>α</i>,20<i>S</i>-trihydroxydammar-24-ene (<b>2</b>) under the same conditions, a mixture of 3- and 12-<i>O</i>-<i>β</i>-D-glucopyranosides <b>19</b> and <b>20</b>.</p>\",\"PeriodicalId\":514,\"journal\":{\"name\":\"Chemistry of Natural Compounds\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.8000,\"publicationDate\":\"2024-09-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Natural Compounds\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10600-024-04464-7\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MEDICINAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Natural Compounds","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10600-024-04464-7","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, MEDICINAL","Score":null,"Total":0}
Synthesis of β-D-Glucopyranosides of 12α-Epimers of 20S-Protopanaxadiol and Betulafolientriol
β-D-Glucopyranosides of 3β, 12α,20S-trihydroxydammar-24-ene (1) and 3α,12α,20S-trihydroxydammar-24-ene (2), close structural analogs of ginsenoside-Rh2 and a metabolite of Panax ginseng glycosides (compound K), were synthesized. Glycosylation of 20S-hydroxydammar-24-ene-3,12-dione (5) and 3α-acetoxy-20S-hydroxydammar-24-en-12-one (6) by 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide (8) under classical Koenig-Knorr reaction conditions followed by deacetylation by NaOMe in MeOH gave free 20-O-β-D-glucopyranosides 10 and 13, treatment of which with NaBH4 in i-PrOH formed 20-O-β-D- glucopyranosides of the 12α-epimers of 20S-protopanaxadiol 11 and betulafolientriol 14. Condensation of 3β,12α,20S-trihydroxydammar-24-ene (1) and glycosyl donor 8 in the presence of Ag2O in CH2Cl2 followed by removal of the protecting groups gave 3-O-β-D-glucopyranoside 16; of 3α,12α,20S-trihydroxydammar-24-ene (2) under the same conditions, a mixture of 3- and 12-O-β-D-glucopyranosides 19 and 20.
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Chemistry of Natural Compounds publishes reviews and general articles about the structure of different classes of natural compounds, the chemical characteristics of botanical families, genus, and species, to establish the comparative laws and connection between physiological activity and the structure of substances.
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