The reaction of β,γ−epoxy alcohols with titanium(III) reagents. A proposed role for intramolecular hydrogen bonding
β,γ-Epoxy alcohols are unique substrates for ring-opening reactions with titanium(III) reagents. The site selectivity of the initial radical-forming step as well as the nature and selectivity of reactions of the resultant carbon-centered radicals are often reversed from those observed for non-hydrox...
Gespeichert in:
| Veröffentlicht in: | Tetrahedron 2019-11, Vol.75 (45), p.130662, Article 130662 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | |
|---|---|
| container_issue | 45 |
| container_start_page | 130662 |
| container_title | Tetrahedron |
| container_volume | 75 |
| creator | Klare, Sven Gordon, Jonathan P. Gansäuer, Andreas RajanBabu, T.V. Nugent, William A. |
| description | β,γ-Epoxy alcohols are unique substrates for ring-opening reactions with titanium(III) reagents. The site selectivity of the initial radical-forming step as well as the nature and selectivity of reactions of the resultant carbon-centered radicals are often reversed from those observed for non-hydroxyl-containing epoxides. In this Report we critically review previous mechanistic proposals regarding these effects and propose an alternative explanation, which implicates intramolecular hydrogen bonding as a key control element.
[Display omitted] |
| doi_str_mv | 10.1016/j.tet.2019.130662 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_7322769</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S0040402019310312</els_id><sourcerecordid>2419098365</sourcerecordid><originalsourceid>FETCH-LOGICAL-c451t-f8f2ba1cbae9ea0f67c6824dd9accc9e81eebc459933eb42780885056df826e43</originalsourceid><addsrcrecordid>eNp9kU1u1DAYhi0EokPhAGyQl0UiwXYcTywkpKriZ6RKbMracpwvE48SO9hOy9yANUeBe_QQnASPplSwYWVZft7Xn74HoeeUlJRQ8XpXJkglI1SWtCJCsAdoRbngRc2peIhWhHBScMLICXoS444QQimrHqOTiglCa8pW6OZqABxAm2S9w77Htz9e3f789e07zP7rHuvR-MGPEd_YNOBkk3Z2mc42m83LQ2oLLsUSn-M5-NlH6HDwI-DeB2xdCnrKN7OMOuBh3wWfcdx611m3fYoe9XqM8OzuPEWf37-7uvhYXH76sLk4vywMr2kq-qZnraam1SBBk16sjWgY7zqpjTESGgrQZlTKqoKWs3VDmqYmtej6hgng1Sl6e-ydl3aCzsBhrFHNwU467JXXVv374uygtv5arSvG1kLmgrO7guC_LBCTmmw0MI7agV-iYpxKIptK1BmlR9QEH2OA_v4bStRBmNqpLEwdhKmjsJx58fd894k_hjLw5ghA3tK1haCiseAMdDaASarz9j_1vwH-DKvZ</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2419098365</pqid></control><display><type>article</type><title>The reaction of β,γ−epoxy alcohols with titanium(III) reagents. A proposed role for intramolecular hydrogen bonding</title><source>Elsevier ScienceDirect Journals</source><creator>Klare, Sven ; Gordon, Jonathan P. ; Gansäuer, Andreas ; RajanBabu, T.V. ; Nugent, William A.</creator><creatorcontrib>Klare, Sven ; Gordon, Jonathan P. ; Gansäuer, Andreas ; RajanBabu, T.V. ; Nugent, William A.</creatorcontrib><description>β,γ-Epoxy alcohols are unique substrates for ring-opening reactions with titanium(III) reagents. The site selectivity of the initial radical-forming step as well as the nature and selectivity of reactions of the resultant carbon-centered radicals are often reversed from those observed for non-hydroxyl-containing epoxides. In this Report we critically review previous mechanistic proposals regarding these effects and propose an alternative explanation, which implicates intramolecular hydrogen bonding as a key control element.
[Display omitted]</description><identifier>ISSN: 0040-4020</identifier><identifier>EISSN: 1464-5416</identifier><identifier>DOI: 10.1016/j.tet.2019.130662</identifier><identifier>PMID: 32601512</identifier><language>eng</language><publisher>England: Elsevier Ltd</publisher><subject>Epoxides ; Free radicals ; Hydrogen bonding ; Mechanism ; Titanium(III)</subject><ispartof>Tetrahedron, 2019-11, Vol.75 (45), p.130662, Article 130662</ispartof><rights>2019 Elsevier Ltd</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c451t-f8f2ba1cbae9ea0f67c6824dd9accc9e81eebc459933eb42780885056df826e43</citedby><cites>FETCH-LOGICAL-c451t-f8f2ba1cbae9ea0f67c6824dd9accc9e81eebc459933eb42780885056df826e43</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S0040402019310312$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>230,314,776,780,881,3537,27901,27902,65306</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/32601512$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Klare, Sven</creatorcontrib><creatorcontrib>Gordon, Jonathan P.</creatorcontrib><creatorcontrib>Gansäuer, Andreas</creatorcontrib><creatorcontrib>RajanBabu, T.V.</creatorcontrib><creatorcontrib>Nugent, William A.</creatorcontrib><title>The reaction of β,γ−epoxy alcohols with titanium(III) reagents. A proposed role for intramolecular hydrogen bonding</title><title>Tetrahedron</title><addtitle>Tetrahedron</addtitle><description>β,γ-Epoxy alcohols are unique substrates for ring-opening reactions with titanium(III) reagents. The site selectivity of the initial radical-forming step as well as the nature and selectivity of reactions of the resultant carbon-centered radicals are often reversed from those observed for non-hydroxyl-containing epoxides. In this Report we critically review previous mechanistic proposals regarding these effects and propose an alternative explanation, which implicates intramolecular hydrogen bonding as a key control element.
[Display omitted]</description><subject>Epoxides</subject><subject>Free radicals</subject><subject>Hydrogen bonding</subject><subject>Mechanism</subject><subject>Titanium(III)</subject><issn>0040-4020</issn><issn>1464-5416</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNp9kU1u1DAYhi0EokPhAGyQl0UiwXYcTywkpKriZ6RKbMracpwvE48SO9hOy9yANUeBe_QQnASPplSwYWVZft7Xn74HoeeUlJRQ8XpXJkglI1SWtCJCsAdoRbngRc2peIhWhHBScMLICXoS444QQimrHqOTiglCa8pW6OZqABxAm2S9w77Htz9e3f789e07zP7rHuvR-MGPEd_YNOBkk3Z2mc42m83LQ2oLLsUSn-M5-NlH6HDwI-DeB2xdCnrKN7OMOuBh3wWfcdx611m3fYoe9XqM8OzuPEWf37-7uvhYXH76sLk4vywMr2kq-qZnraam1SBBk16sjWgY7zqpjTESGgrQZlTKqoKWs3VDmqYmtej6hgng1Sl6e-ydl3aCzsBhrFHNwU467JXXVv374uygtv5arSvG1kLmgrO7guC_LBCTmmw0MI7agV-iYpxKIptK1BmlR9QEH2OA_v4bStRBmNqpLEwdhKmjsJx58fd894k_hjLw5ghA3tK1haCiseAMdDaASarz9j_1vwH-DKvZ</recordid><startdate>20191108</startdate><enddate>20191108</enddate><creator>Klare, Sven</creator><creator>Gordon, Jonathan P.</creator><creator>Gansäuer, Andreas</creator><creator>RajanBabu, T.V.</creator><creator>Nugent, William A.</creator><general>Elsevier Ltd</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>5PM</scope></search><sort><creationdate>20191108</creationdate><title>The reaction of β,γ−epoxy alcohols with titanium(III) reagents. A proposed role for intramolecular hydrogen bonding</title><author>Klare, Sven ; Gordon, Jonathan P. ; Gansäuer, Andreas ; RajanBabu, T.V. ; Nugent, William A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c451t-f8f2ba1cbae9ea0f67c6824dd9accc9e81eebc459933eb42780885056df826e43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Epoxides</topic><topic>Free radicals</topic><topic>Hydrogen bonding</topic><topic>Mechanism</topic><topic>Titanium(III)</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Klare, Sven</creatorcontrib><creatorcontrib>Gordon, Jonathan P.</creatorcontrib><creatorcontrib>Gansäuer, Andreas</creatorcontrib><creatorcontrib>RajanBabu, T.V.</creatorcontrib><creatorcontrib>Nugent, William A.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Tetrahedron</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Klare, Sven</au><au>Gordon, Jonathan P.</au><au>Gansäuer, Andreas</au><au>RajanBabu, T.V.</au><au>Nugent, William A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The reaction of β,γ−epoxy alcohols with titanium(III) reagents. A proposed role for intramolecular hydrogen bonding</atitle><jtitle>Tetrahedron</jtitle><addtitle>Tetrahedron</addtitle><date>2019-11-08</date><risdate>2019</risdate><volume>75</volume><issue>45</issue><spage>130662</spage><pages>130662-</pages><artnum>130662</artnum><issn>0040-4020</issn><eissn>1464-5416</eissn><abstract>β,γ-Epoxy alcohols are unique substrates for ring-opening reactions with titanium(III) reagents. The site selectivity of the initial radical-forming step as well as the nature and selectivity of reactions of the resultant carbon-centered radicals are often reversed from those observed for non-hydroxyl-containing epoxides. In this Report we critically review previous mechanistic proposals regarding these effects and propose an alternative explanation, which implicates intramolecular hydrogen bonding as a key control element.
[Display omitted]</abstract><cop>England</cop><pub>Elsevier Ltd</pub><pmid>32601512</pmid><doi>10.1016/j.tet.2019.130662</doi><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0040-4020 |
| ispartof | Tetrahedron, 2019-11, Vol.75 (45), p.130662, Article 130662 |
| issn | 0040-4020 1464-5416 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_7322769 |
| source | Elsevier ScienceDirect Journals |
| subjects | Epoxides Free radicals Hydrogen bonding Mechanism Titanium(III) |
| title | The reaction of β,γ−epoxy alcohols with titanium(III) reagents. A proposed role for intramolecular hydrogen bonding |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-03T19%3A54%3A50IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=The%20reaction%20of%20%CE%B2,%CE%B3%E2%88%92epoxy%20alcohols%20with%20titanium(III)%20reagents.%20A%20proposed%20role%20for%20intramolecular%20hydrogen%20bonding&rft.jtitle=Tetrahedron&rft.au=Klare,%20Sven&rft.date=2019-11-08&rft.volume=75&rft.issue=45&rft.spage=130662&rft.pages=130662-&rft.artnum=130662&rft.issn=0040-4020&rft.eissn=1464-5416&rft_id=info:doi/10.1016/j.tet.2019.130662&rft_dat=%3Cproquest_pubme%3E2419098365%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2419098365&rft_id=info:pmid/32601512&rft_els_id=S0040402019310312&rfr_iscdi=true |