Chiral decalins : preparation from oleanolic acid and application in the synthesis of (-)-9-epi-ambrox
A novel and versatile process was developed to prepare the trans-decalins Delta9(11)-3beta-acetoxysclareolide (2) and Delta9(11)-3beta-acetoxy-8-epi-sclareolide (3), respectively, with 4a-methoxycarbonyl-2,7,7-trimethyl-1-oxo-cis-decalin-2-ene (4) and its C-3 hydroxyl derivative 5 from oleanolic acid (3beta-hydroxyolean-12-en-28-oic acid, 1). Three key steps were (a) introduction of the AcO-12 group and the C-9,C-11 double bond at ring C of methyl 3beta-acetoxyolean-12-en-28-oate (8) to afford the diene, methyl 3,12-diacetoxyolean-9(11),12-dien-28-oate (11); (b) photolytic cleavage of the C-8,C-14 bond in the diene to give an acetoxy-substituted triene 14; and (c) oxidative cleavage of the triene or its hydrolyzed alpha,beta-unsaturated ketone product with m-CPBA/TsOH to give the cis- and trans-decalins 2-5. Delata9(11)-3beta-Acetoxysclareolide (2) was stereospecifically reduced to give 3beta-acetoxy-9-epi-sclareolide (23), from which (-)-9-epi-ambrox (7) was synthesized.
| Medienart: |
Artikel |
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| Erscheinungsjahr: |
2006 |
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| Erschienen: |
2006 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:69 |
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| Enthalten in: |
Journal of natural products - 69(2006), 11 vom: 13. Nov., Seite 1531-8 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Yang, Hai-Jun [VerfasserIn] |
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| Themen: |
65588-69-4 |
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| Anmerkungen: |
Date Completed 12.02.2007 Date Revised 21.11.2013 published: Print Citation Status MEDLINE |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM166779814 |
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| 041 | |a eng | ||
| 100 | 1 | |a Yang, Hai-Jun |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Chiral decalins |b preparation from oleanolic acid and application in the synthesis of (-)-9-epi-ambrox |
| 264 | 1 | |c 2006 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ohne Hilfsmittel zu benutzen |b n |2 rdamedia | ||
| 338 | |a Band |b nc |2 rdacarrier | ||
| 500 | |a Date Completed 12.02.2007 | ||
| 500 | |a Date Revised 21.11.2013 | ||
| 500 | |a published: Print | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a A novel and versatile process was developed to prepare the trans-decalins Delta9(11)-3beta-acetoxysclareolide (2) and Delta9(11)-3beta-acetoxy-8-epi-sclareolide (3), respectively, with 4a-methoxycarbonyl-2,7,7-trimethyl-1-oxo-cis-decalin-2-ene (4) and its C-3 hydroxyl derivative 5 from oleanolic acid (3beta-hydroxyolean-12-en-28-oic acid, 1). Three key steps were (a) introduction of the AcO-12 group and the C-9,C-11 double bond at ring C of methyl 3beta-acetoxyolean-12-en-28-oate (8) to afford the diene, methyl 3,12-diacetoxyolean-9(11),12-dien-28-oate (11); (b) photolytic cleavage of the C-8,C-14 bond in the diene to give an acetoxy-substituted triene 14; and (c) oxidative cleavage of the triene or its hydrolyzed alpha,beta-unsaturated ketone product with m-CPBA/TsOH to give the cis- and trans-decalins 2-5. Delata9(11)-3beta-Acetoxysclareolide (2) was stereospecifically reduced to give 3beta-acetoxy-9-epi-sclareolide (23), from which (-)-9-epi-ambrox (7) was synthesized | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 7 | |a Furans |2 NLM | |
| 650 | 7 | |a Naphthalenes |2 NLM | |
| 650 | 7 | |a ambrox |2 NLM | |
| 650 | 7 | |a 65588-69-4 |2 NLM | |
| 650 | 7 | |a Oleanolic Acid |2 NLM | |
| 650 | 7 | |a 6SMK8R7TGJ |2 NLM | |
| 650 | 7 | |a decalin |2 NLM | |
| 650 | 7 | |a 88451Q4XYF |2 NLM | |
| 700 | 1 | |a Li, Bo-Gang |e verfasserin |4 aut | |
| 700 | 1 | |a Cai, Xiao-Hua |e verfasserin |4 aut | |
| 700 | 1 | |a Qi, Hua-Yi |e verfasserin |4 aut | |
| 700 | 1 | |a Luo, Ying-Gang |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Guo-Lin |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Journal of natural products |d 1979 |g 69(2006), 11 vom: 13. Nov., Seite 1531-8 |w (DE-627)NLM000924377 |x 1520-6025 |7 nnns |
| 773 | 1 | 8 | |g volume:69 |g year:2006 |g number:11 |g day:13 |g month:11 |g pages:1531-8 |
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