Effect of Intramolecular Paternò-Büchi Reaction on the Thermodynamics and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional Polycycles
In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the...
Gespeichert in:
| Veröffentlicht in: | Journal of organic chemistry 2009-05, Vol.74 (9), p.3484-3490 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 3490 |
|---|---|
| container_issue | 9 |
| container_start_page | 3484 |
| container_title | Journal of organic chemistry |
| container_volume | 74 |
| creator | VALIULIN, Roman A DRESSEN, Donald G RIGGS, Jennifer R HABTE, Faven M KUTATELADZE, Andrei G |
| description | In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier. |
| doi_str_mv | 10.1021/jo9003822 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_67163669</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>67163669</sourcerecordid><originalsourceid>FETCH-LOGICAL-c313t-492ff388ca2d4a4141ea718ef7a6da913fc19a9759daa7863c62e9124f7b3c923</originalsourceid><addsrcrecordid>eNpFkc9qFTEUh4Mo9lpd-AKSjQXBqfkzk5kstbZaLFpsXYkMp5mT3pRMcptkwHkUX8N1d30xp_RSDwcOP_j4FudHyEvO9jkT_N1V1IzJTohHZMUbwSqlWf2YrBgTopJCyR3yLOcrtkzTNE_JDteyrrlsVuTPobVoCo2WHoeSYIwezeQh0VMomMLt3-rD7Y1ZO_odwRQXA122rJGerzGNcZgDjM5kCmGgX1zAchcW21eE5Gf6ES8xYFpc9Kd8K39VZ-5yhJLixhl6tna2UBfokZ9-L2rw9DT62czGY35OnljwGV9s7y75cXR4fvC5Ovn26fjg_UllJJelqrWwVnadATHUUPOaI7S8Q9uCGkBzaQ3XoNtGDwBtp6RRAjUXtW0vpNFC7pK9e-8mxesJc-lHlw16DwHjlHvVciWV0gv45h40Keac0Pab5EZIc89Zf9dD_9DDwr7aSqeLEYf_5PbxC_B6C0A24G2CYFx-4ASvRSN1I_8BU3qS1Q</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>67163669</pqid></control><display><type>article</type><title>Effect of Intramolecular Paternò-Büchi Reaction on the Thermodynamics and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional Polycycles</title><source>American Chemical Society Journals</source><creator>VALIULIN, Roman A ; DRESSEN, Donald G ; RIGGS, Jennifer R ; HABTE, Faven M ; KUTATELADZE, Andrei G</creator><creatorcontrib>VALIULIN, Roman A ; DRESSEN, Donald G ; RIGGS, Jennifer R ; HABTE, Faven M ; KUTATELADZE, Andrei G</creatorcontrib><description>In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo9003822</identifier><identifier>PMID: 19344135</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Alicyclic compounds ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; Chemistry ; Exact sciences and technology ; Heterocyclic compounds ; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives ; Kinetics and mechanisms ; Organic chemistry ; Preparations and properties ; Reactivity and mechanisms</subject><ispartof>Journal of organic chemistry, 2009-05, Vol.74 (9), p.3484-3490</ispartof><rights>2009 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c313t-492ff388ca2d4a4141ea718ef7a6da913fc19a9759daa7863c62e9124f7b3c923</citedby><cites>FETCH-LOGICAL-c313t-492ff388ca2d4a4141ea718ef7a6da913fc19a9759daa7863c62e9124f7b3c923</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,2752,27901,27902</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=21425395$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/19344135$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>VALIULIN, Roman A</creatorcontrib><creatorcontrib>DRESSEN, Donald G</creatorcontrib><creatorcontrib>RIGGS, Jennifer R</creatorcontrib><creatorcontrib>HABTE, Faven M</creatorcontrib><creatorcontrib>KUTATELADZE, Andrei G</creatorcontrib><title>Effect of Intramolecular Paternò-Büchi Reaction on the Thermodynamics and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional Polycycles</title><title>Journal of organic chemistry</title><addtitle>J Org Chem</addtitle><description>In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier.</description><subject>Alicyclic compounds</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Heterocyclic compounds</subject><subject>Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives</subject><subject>Kinetics and mechanisms</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Reactivity and mechanisms</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNpFkc9qFTEUh4Mo9lpd-AKSjQXBqfkzk5kstbZaLFpsXYkMp5mT3pRMcptkwHkUX8N1d30xp_RSDwcOP_j4FudHyEvO9jkT_N1V1IzJTohHZMUbwSqlWf2YrBgTopJCyR3yLOcrtkzTNE_JDteyrrlsVuTPobVoCo2WHoeSYIwezeQh0VMomMLt3-rD7Y1ZO_odwRQXA122rJGerzGNcZgDjM5kCmGgX1zAchcW21eE5Gf6ES8xYFpc9Kd8K39VZ-5yhJLixhl6tna2UBfokZ9-L2rw9DT62czGY35OnljwGV9s7y75cXR4fvC5Ovn26fjg_UllJJelqrWwVnadATHUUPOaI7S8Q9uCGkBzaQ3XoNtGDwBtp6RRAjUXtW0vpNFC7pK9e-8mxesJc-lHlw16DwHjlHvVciWV0gv45h40Keac0Pab5EZIc89Zf9dD_9DDwr7aSqeLEYf_5PbxC_B6C0A24G2CYFx-4ASvRSN1I_8BU3qS1Q</recordid><startdate>20090501</startdate><enddate>20090501</enddate><creator>VALIULIN, Roman A</creator><creator>DRESSEN, Donald G</creator><creator>RIGGS, Jennifer R</creator><creator>HABTE, Faven M</creator><creator>KUTATELADZE, Andrei G</creator><general>American Chemical Society</general><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20090501</creationdate><title>Effect of Intramolecular Paternò-Büchi Reaction on the Thermodynamics and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional Polycycles</title><author>VALIULIN, Roman A ; DRESSEN, Donald G ; RIGGS, Jennifer R ; HABTE, Faven M ; KUTATELADZE, Andrei G</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c313t-492ff388ca2d4a4141ea718ef7a6da913fc19a9759daa7863c62e9124f7b3c923</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>Alicyclic compounds</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Heterocyclic compounds</topic><topic>Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives</topic><topic>Kinetics and mechanisms</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>VALIULIN, Roman A</creatorcontrib><creatorcontrib>DRESSEN, Donald G</creatorcontrib><creatorcontrib>RIGGS, Jennifer R</creatorcontrib><creatorcontrib>HABTE, Faven M</creatorcontrib><creatorcontrib>KUTATELADZE, Andrei G</creatorcontrib><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>VALIULIN, Roman A</au><au>DRESSEN, Donald G</au><au>RIGGS, Jennifer R</au><au>HABTE, Faven M</au><au>KUTATELADZE, Andrei G</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Effect of Intramolecular Paternò-Büchi Reaction on the Thermodynamics and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional Polycycles</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J Org Chem</addtitle><date>2009-05-01</date><risdate>2009</risdate><volume>74</volume><issue>9</issue><spage>3484</spage><epage>3490</epage><pages>3484-3490</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>19344135</pmid><doi>10.1021/jo9003822</doi><tpages>7</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0022-3263 |
| ispartof | Journal of organic chemistry, 2009-05, Vol.74 (9), p.3484-3490 |
| issn | 0022-3263 1520-6904 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_67163669 |
| source | American Chemical Society Journals |
| subjects | Alicyclic compounds Alicyclic compounds, terpenoids, prostaglandins, steroids Chemistry Exact sciences and technology Heterocyclic compounds Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives Kinetics and mechanisms Organic chemistry Preparations and properties Reactivity and mechanisms |
| title | Effect of Intramolecular Paternò-Büchi Reaction on the Thermodynamics and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional Polycycles |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-08T00%3A39%3A43IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Effect%20of%20Intramolecular%20Patern%C3%B2-B%C3%BCchi%20Reaction%20on%20the%20Thermodynamics%20and%20Kinetics%20of%20Nearly%20Degenerate%20%5B3,3%5D-Sigmatropic%20Shift%20in%20Fluxional%20Polycycles&rft.jtitle=Journal%20of%20organic%20chemistry&rft.au=VALIULIN,%20Roman%20A&rft.date=2009-05-01&rft.volume=74&rft.issue=9&rft.spage=3484&rft.epage=3490&rft.pages=3484-3490&rft.issn=0022-3263&rft.eissn=1520-6904&rft.coden=JOCEAH&rft_id=info:doi/10.1021/jo9003822&rft_dat=%3Cproquest_cross%3E67163669%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=67163669&rft_id=info:pmid/19344135&rfr_iscdi=true |