General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion
A stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary...
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| Format: | Article |
| Language: | English |
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MDPI AG
2017-06-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/22/7/1041 |
| _version_ | 1818984710592790528 |
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| author | Hilan Z. Kaplan Victor L. Rendina Jason S. Kingsbury |
| author_facet | Hilan Z. Kaplan Victor L. Rendina Jason S. Kingsbury |
| author_sort | Hilan Z. Kaplan |
| collection | DOAJ |
| description | A stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary and all-carbon-substituted. Also featured is a highly regioselective diazoalkane—carbonyl homologation reaction to prepare the 6,6-bicyclic skeleton. Therein, the utility of Sc(OTf)3 as a mild catalyst for formal 1C insertion in complex settings is demonstrated. |
| first_indexed | 2024-12-20T18:23:20Z |
| format | Article |
| id | doaj.art-70e73ebb3e904ac985dc97a8c8cb427e |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-20T18:23:20Z |
| publishDate | 2017-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-70e73ebb3e904ac985dc97a8c8cb427e2022-12-21T19:30:13ZengMDPI AGMolecules1420-30492017-06-01227104110.3390/molecules22071041molecules22071041General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring ExpansionHilan Z. Kaplan0Victor L. Rendina1Jason S. Kingsbury2Eugene F. Merkert Chemistry Center, Boston College, 2609 Beacon Street, Chestnut Hill, MA 02467, USAEugene F. Merkert Chemistry Center, Boston College, 2609 Beacon Street, Chestnut Hill, MA 02467, USAAhmanson Science Center, California Lutheran University, 60 West Olsen Rd., Thousand Oaks, CA 91360, USAA stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary and all-carbon-substituted. Also featured is a highly regioselective diazoalkane—carbonyl homologation reaction to prepare the 6,6-bicyclic skeleton. Therein, the utility of Sc(OTf)3 as a mild catalyst for formal 1C insertion in complex settings is demonstrated.http://www.mdpi.com/1420-3049/22/7/1041quinone natural productsquaternary carbon synthesiscis-decalinscandium triflatecatalytic ring expansionhomologation(trimethylsilyl)diazomethanehexahydroindanones5-epi-ilimaquinone5-epi-isospongiaquinone |
| spellingShingle | Hilan Z. Kaplan Victor L. Rendina Jason S. Kingsbury General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion Molecules quinone natural products quaternary carbon synthesis cis-decalin scandium triflate catalytic ring expansion homologation (trimethylsilyl)diazomethane hexahydroindanones 5-epi-ilimaquinone 5-epi-isospongiaquinone |
| title | General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion |
| title_full | General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion |
| title_fullStr | General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion |
| title_full_unstemmed | General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion |
| title_short | General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion |
| title_sort | general methodologies toward cis fused quinone sesquiterpenoids enantiospecific synthesis of the epi ilimaquinone core featuring sc catalyzed ring expansion |
| topic | quinone natural products quaternary carbon synthesis cis-decalin scandium triflate catalytic ring expansion homologation (trimethylsilyl)diazomethane hexahydroindanones 5-epi-ilimaquinone 5-epi-isospongiaquinone |
| url | http://www.mdpi.com/1420-3049/22/7/1041 |
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