Selective Ring Contraction of 5-Spirocyclopropane Isoxazolidines Mediated by Acids
Thermolysis of 3,4-cis ring-fused 5-spirocyclopropane isoxazolidines 16, 18−21, 33, 34, 38a, and 61, in the presence of a protic acid at 70−110 °C, yielded 3,4-cis ring-fused azetidin-2-ones 22−26, 41, 42, 46, and 62 with concomitant extrusion of ethylene, in good yields. So far, the collected evide...
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| Veröffentlicht in: | Journal of organic chemistry 2003-04, Vol.68 (8), p.3271-3280 |
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| container_title | Journal of organic chemistry |
| container_volume | 68 |
| creator | Cordero, Franca M Pisaneschi, Federica Salvati, Maria Paschetta, Valentina Ollivier, Jean Salaün, Jacques Brandi, Alberto |
| description | Thermolysis of 3,4-cis ring-fused 5-spirocyclopropane isoxazolidines 16, 18−21, 33, 34, 38a, and 61, in the presence of a protic acid at 70−110 °C, yielded 3,4-cis ring-fused azetidin-2-ones 22−26, 41, 42, 46, and 62 with concomitant extrusion of ethylene, in good yields. So far, the collected evidences strongly support a mechanism started by a homolytic cleavage of the protonated N−O bond for the rearrangement of 5-spirocyclopropane isoxazolidines to β-lactams. Some different competitive pathways can then follow depending on the stability or the stereoelectronic properties of cationic diradical intermediates. The two-step process, intramolecular 1,3-dipolar cycloaddition/thermal rearrangement under acidic conditions, represents a general synthesis of a new class of 3,4-cis-fused bicyclic azetidin-2-ones starting from easily available compounds such as amino acids, hydroxy acids, and dicarbonyl or amino alcohol derivatives. |
| doi_str_mv | 10.1021/jo034003g |
| format | Article |
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So far, the collected evidences strongly support a mechanism started by a homolytic cleavage of the protonated N−O bond for the rearrangement of 5-spirocyclopropane isoxazolidines to β-lactams. Some different competitive pathways can then follow depending on the stability or the stereoelectronic properties of cationic diradical intermediates. The two-step process, intramolecular 1,3-dipolar cycloaddition/thermal rearrangement under acidic conditions, represents a general synthesis of a new class of 3,4-cis-fused bicyclic azetidin-2-ones starting from easily available compounds such as amino acids, hydroxy acids, and dicarbonyl or amino alcohol derivatives.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo034003g</identifier><identifier>PMID: 12688801</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Chemistry ; Exact sciences and technology ; Heterocyclic compounds ; Heterocyclic compounds with only one n hetero atom and condensed derivatives ; Organic chemistry ; Preparations and properties</subject><ispartof>Journal of organic chemistry, 2003-04, Vol.68 (8), p.3271-3280</ispartof><rights>Copyright © 2003 American Chemical Society</rights><rights>2003 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a445t-dd922ab0e4230976590e00cbb83934a7c0ebce6eabb48e6c58c2887cd7e1b8ee3</citedby><cites>FETCH-LOGICAL-a445t-dd922ab0e4230976590e00cbb83934a7c0ebce6eabb48e6c58c2887cd7e1b8ee3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo034003g$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo034003g$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=14742412$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/12688801$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Cordero, Franca M</creatorcontrib><creatorcontrib>Pisaneschi, Federica</creatorcontrib><creatorcontrib>Salvati, Maria</creatorcontrib><creatorcontrib>Paschetta, Valentina</creatorcontrib><creatorcontrib>Ollivier, Jean</creatorcontrib><creatorcontrib>Salaün, Jacques</creatorcontrib><creatorcontrib>Brandi, Alberto</creatorcontrib><title>Selective Ring Contraction of 5-Spirocyclopropane Isoxazolidines Mediated by Acids</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Thermolysis of 3,4-cis ring-fused 5-spirocyclopropane isoxazolidines 16, 18−21, 33, 34, 38a, and 61, in the presence of a protic acid at 70−110 °C, yielded 3,4-cis ring-fused azetidin-2-ones 22−26, 41, 42, 46, and 62 with concomitant extrusion of ethylene, in good yields. So far, the collected evidences strongly support a mechanism started by a homolytic cleavage of the protonated N−O bond for the rearrangement of 5-spirocyclopropane isoxazolidines to β-lactams. Some different competitive pathways can then follow depending on the stability or the stereoelectronic properties of cationic diradical intermediates. 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Org. Chem</addtitle><date>2003-04-18</date><risdate>2003</risdate><volume>68</volume><issue>8</issue><spage>3271</spage><epage>3280</epage><pages>3271-3280</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Thermolysis of 3,4-cis ring-fused 5-spirocyclopropane isoxazolidines 16, 18−21, 33, 34, 38a, and 61, in the presence of a protic acid at 70−110 °C, yielded 3,4-cis ring-fused azetidin-2-ones 22−26, 41, 42, 46, and 62 with concomitant extrusion of ethylene, in good yields. So far, the collected evidences strongly support a mechanism started by a homolytic cleavage of the protonated N−O bond for the rearrangement of 5-spirocyclopropane isoxazolidines to β-lactams. Some different competitive pathways can then follow depending on the stability or the stereoelectronic properties of cationic diradical intermediates. The two-step process, intramolecular 1,3-dipolar cycloaddition/thermal rearrangement under acidic conditions, represents a general synthesis of a new class of 3,4-cis-fused bicyclic azetidin-2-ones starting from easily available compounds such as amino acids, hydroxy acids, and dicarbonyl or amino alcohol derivatives.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>12688801</pmid><doi>10.1021/jo034003g</doi><tpages>10</tpages></addata></record> |
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| subjects | Chemistry Exact sciences and technology Heterocyclic compounds Heterocyclic compounds with only one n hetero atom and condensed derivatives Organic chemistry Preparations and properties |
| title | Selective Ring Contraction of 5-Spirocyclopropane Isoxazolidines Mediated by Acids |
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