Synthesis of heteroarenes using cascade radical cyclisation via iminyl radicals
Cascade radical cyclisation involving homolytic aromatic substitution has been used to synthesise new tetracycles. Treatment of vinyl iodide radical precursors with Me(3)Sn. radicals (from hexamethylditin) yielded intermediate vinyl radicals which undergo 5-exo cyclisation onto suitably placed nitri...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2005-04, Vol.3 (8), p.1460-1467 |
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| container_title | Organic & biomolecular chemistry |
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| creator | Bowman, W Russell Cloonan, Martin O Fletcher, Anthony J Stein, Tobias |
| description | Cascade radical cyclisation involving homolytic aromatic substitution has been used to synthesise new tetracycles. Treatment of vinyl iodide radical precursors with Me(3)Sn. radicals (from hexamethylditin) yielded intermediate vinyl radicals which undergo 5-exo cyclisation onto suitably placed nitrile groups to yield intermediate iminyl radicals. The iminyl radicals undergo aromatic homolytic substitution via 6-endo cyclisation (or 5-exo cyclisation followed by neophyl rearrangement) with loss of hydrogen (H.) in a H-abstraction step. We propose that this abstraction was facilitated by tert-butoxyl (t-BuO.) radicals from di-tert-butyl peroxide or methyl radicals, generated from breakdown of trimethylstannyl radicals (Me(3)Sn.). The biologically active alkaloids mappicine and luotonin A were synthesised using the new methodology. A novel radical conversion of nitriles to primary amides is proposed. |
| doi_str_mv | 10.1039/b501509j |
| format | Article |
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Treatment of vinyl iodide radical precursors with Me(3)Sn. radicals (from hexamethylditin) yielded intermediate vinyl radicals which undergo 5-exo cyclisation onto suitably placed nitrile groups to yield intermediate iminyl radicals. The iminyl radicals undergo aromatic homolytic substitution via 6-endo cyclisation (or 5-exo cyclisation followed by neophyl rearrangement) with loss of hydrogen (H.) in a H-abstraction step. We propose that this abstraction was facilitated by tert-butoxyl (t-BuO.) radicals from di-tert-butyl peroxide or methyl radicals, generated from breakdown of trimethylstannyl radicals (Me(3)Sn.). The biologically active alkaloids mappicine and luotonin A were synthesised using the new methodology. A novel radical conversion of nitriles to primary amides is proposed.</description><identifier>ISSN: 1477-0520</identifier><identifier>EISSN: 1477-0539</identifier><identifier>DOI: 10.1039/b501509j</identifier><identifier>PMID: 15827642</identifier><language>eng</language><publisher>England</publisher><subject>Alkaloids - chemical synthesis ; Alkaloids - chemistry ; Cyclization ; Free Radicals - chemistry ; Imides - chemistry ; Indolizines - chemical synthesis ; Indolizines - chemistry ; Molecular Structure ; Pyrroles - chemical synthesis ; Pyrroles - chemistry ; Quinolines - chemical synthesis ; Quinolines - chemistry ; Quinones - chemical synthesis ; Quinones - chemistry</subject><ispartof>Organic & biomolecular chemistry, 2005-04, Vol.3 (8), p.1460-1467</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c281t-2b48f12e165fd8b4f03e880131e8c65188d66086537456760ba2d3991f60f8e73</citedby><cites>FETCH-LOGICAL-c281t-2b48f12e165fd8b4f03e880131e8c65188d66086537456760ba2d3991f60f8e73</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,2829,27923,27924</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15827642$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Bowman, W Russell</creatorcontrib><creatorcontrib>Cloonan, Martin O</creatorcontrib><creatorcontrib>Fletcher, Anthony J</creatorcontrib><creatorcontrib>Stein, Tobias</creatorcontrib><title>Synthesis of heteroarenes using cascade radical cyclisation via iminyl radicals</title><title>Organic & biomolecular chemistry</title><addtitle>Org Biomol Chem</addtitle><description>Cascade radical cyclisation involving homolytic aromatic substitution has been used to synthesise new tetracycles. Treatment of vinyl iodide radical precursors with Me(3)Sn. radicals (from hexamethylditin) yielded intermediate vinyl radicals which undergo 5-exo cyclisation onto suitably placed nitrile groups to yield intermediate iminyl radicals. The iminyl radicals undergo aromatic homolytic substitution via 6-endo cyclisation (or 5-exo cyclisation followed by neophyl rearrangement) with loss of hydrogen (H.) in a H-abstraction step. We propose that this abstraction was facilitated by tert-butoxyl (t-BuO.) radicals from di-tert-butyl peroxide or methyl radicals, generated from breakdown of trimethylstannyl radicals (Me(3)Sn.). The biologically active alkaloids mappicine and luotonin A were synthesised using the new methodology. A novel radical conversion of nitriles to primary amides is proposed.</description><subject>Alkaloids - chemical synthesis</subject><subject>Alkaloids - chemistry</subject><subject>Cyclization</subject><subject>Free Radicals - chemistry</subject><subject>Imides - chemistry</subject><subject>Indolizines - chemical synthesis</subject><subject>Indolizines - chemistry</subject><subject>Molecular Structure</subject><subject>Pyrroles - chemical synthesis</subject><subject>Pyrroles - chemistry</subject><subject>Quinolines - chemical synthesis</subject><subject>Quinolines - chemistry</subject><subject>Quinones - chemical synthesis</subject><subject>Quinones - chemistry</subject><issn>1477-0520</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpFkEtLAzEYRYMoVqvgL5CsxM1o3skspfiCQhfqeshkvtiUedRkRph_70hbXd0L93AXB6ErSu4o4fl9KQmVJN8coTMqtM6I5PnxX2dkhs5T2hBCc63EKZpRadjU2BlavY1tv4YUEu48XkMPsbMRWkh4SKH9xM4mZyvA0VbB2Rq70dUh2T50Lf4OFocmtGN9mNMFOvFTwOU-5-jj6fF98ZItV8-vi4dl5pihfcZKYTxlQJX0lSmFJxyMIZRTME5JakylFDFKci2k0oqUllU8z6lXxBvQfI5udr_b2H0NkPqiCclBXdsWuiEVSmvBBFMTeLsDXexSiuCLbQyNjWNBSfErrzjIm9Dr_edQNlD9g3tb_AfAjWkO</recordid><startdate>20050421</startdate><enddate>20050421</enddate><creator>Bowman, W Russell</creator><creator>Cloonan, Martin O</creator><creator>Fletcher, Anthony J</creator><creator>Stein, Tobias</creator><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20050421</creationdate><title>Synthesis of heteroarenes using cascade radical cyclisation via iminyl radicals</title><author>Bowman, W Russell ; Cloonan, Martin O ; Fletcher, Anthony J ; Stein, Tobias</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c281t-2b48f12e165fd8b4f03e880131e8c65188d66086537456760ba2d3991f60f8e73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Alkaloids - chemical synthesis</topic><topic>Alkaloids - chemistry</topic><topic>Cyclization</topic><topic>Free Radicals - chemistry</topic><topic>Imides - chemistry</topic><topic>Indolizines - chemical synthesis</topic><topic>Indolizines - chemistry</topic><topic>Molecular Structure</topic><topic>Pyrroles - chemical synthesis</topic><topic>Pyrroles - chemistry</topic><topic>Quinolines - chemical synthesis</topic><topic>Quinolines - chemistry</topic><topic>Quinones - chemical synthesis</topic><topic>Quinones - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bowman, W Russell</creatorcontrib><creatorcontrib>Cloonan, Martin O</creatorcontrib><creatorcontrib>Fletcher, Anthony J</creatorcontrib><creatorcontrib>Stein, Tobias</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Organic & biomolecular chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bowman, W Russell</au><au>Cloonan, Martin O</au><au>Fletcher, Anthony J</au><au>Stein, Tobias</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of heteroarenes using cascade radical cyclisation via iminyl radicals</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2005-04-21</date><risdate>2005</risdate><volume>3</volume><issue>8</issue><spage>1460</spage><epage>1467</epage><pages>1460-1467</pages><issn>1477-0520</issn><eissn>1477-0539</eissn><abstract>Cascade radical cyclisation involving homolytic aromatic substitution has been used to synthesise new tetracycles. Treatment of vinyl iodide radical precursors with Me(3)Sn. radicals (from hexamethylditin) yielded intermediate vinyl radicals which undergo 5-exo cyclisation onto suitably placed nitrile groups to yield intermediate iminyl radicals. The iminyl radicals undergo aromatic homolytic substitution via 6-endo cyclisation (or 5-exo cyclisation followed by neophyl rearrangement) with loss of hydrogen (H.) in a H-abstraction step. We propose that this abstraction was facilitated by tert-butoxyl (t-BuO.) radicals from di-tert-butyl peroxide or methyl radicals, generated from breakdown of trimethylstannyl radicals (Me(3)Sn.). The biologically active alkaloids mappicine and luotonin A were synthesised using the new methodology. A novel radical conversion of nitriles to primary amides is proposed.</abstract><cop>England</cop><pmid>15827642</pmid><doi>10.1039/b501509j</doi><tpages>8</tpages></addata></record> |
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| ispartof | Organic & biomolecular chemistry, 2005-04, Vol.3 (8), p.1460-1467 |
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| source | MEDLINE; Royal Society of Chemistry Journals Archive (1841-2007); Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Alkaloids - chemical synthesis Alkaloids - chemistry Cyclization Free Radicals - chemistry Imides - chemistry Indolizines - chemical synthesis Indolizines - chemistry Molecular Structure Pyrroles - chemical synthesis Pyrroles - chemistry Quinolines - chemical synthesis Quinolines - chemistry Quinones - chemical synthesis Quinones - chemistry |
| title | Synthesis of heteroarenes using cascade radical cyclisation via iminyl radicals |
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