Photochemical Strain‐Release‐Driven Cyclobutylation of C(sp3)‐Centered Radicals
A new photoredox‐catalyzed decarboxylative radical addition approach to functionalized cyclobutanes is described. The reaction involves an unprecedented formal Giese‐type addition of C(sp3)‐centered radicals to highly strained bicyclo[1.1.0]butanes. The mild photoredox conditions, which make use of...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2020-02, Vol.59 (7), p.2618-2622 |
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| creator | Ernouf, Guillaume Chirkin, Egor Rhyman, Lydia Ramasami, Ponnadurai Cintrat, Jean‐Christophe |
| description | A new photoredox‐catalyzed decarboxylative radical addition approach to functionalized cyclobutanes is described. The reaction involves an unprecedented formal Giese‐type addition of C(sp3)‐centered radicals to highly strained bicyclo[1.1.0]butanes. The mild photoredox conditions, which make use of a readily available and bench stable phenyl sulfonyl bicyclo[1.1.0]butane, proved to be amenable to a diverse range of α‐amino and α‐oxy carboxylic acids, providing a concise route to 1,3‐disubstituted cyclobutanes. Furthermore, kinetic studies and DFT calculations unveiled mechanistic details on bicyclo[1.1.0]butane reactivity relative to the corresponding olefin system.
High‐lying SOMO radicals, generated in situ under visible‐light photoredox conditions, undergo an efficient addition to highly strained bicyclo[1.1.0]butanes, providing a straightforward access to valuable alkylated cyclobutanes. |
| doi_str_mv | 10.1002/anie.201908951 |
| format | Article |
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High‐lying SOMO radicals, generated in situ under visible‐light photoredox conditions, undergo an efficient addition to highly strained bicyclo[1.1.0]butanes, providing a straightforward access to valuable alkylated cyclobutanes.</description><subject>bicyclo[1.1.0]butanes</subject><subject>Butane</subject><subject>Butanes</subject><subject>Carboxylic acids</subject><subject>Chemical Sciences</subject><subject>cyclobutanes</subject><subject>late-stage functionalization</subject><subject>photocatalysis</subject><subject>Photochemicals</subject><subject>Radicals</subject><subject>strained molecules</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNqF0cFq3DAQBmARWpI07bXHYsglOXgzsixLOi5O2gSWNqTNWcjymFXwWhvJTtlbH6HP2Ceplk03kEtPGoZPPxI_IR8pzChAcWEGh7MCqAKpOD0gx5QXNGdCsDdpLhnLheT0iLyL8SF5KaE6JEeMcqWAyWNyf7v0o7dLXDlr-uz7GIwb_vz6fYc9mohpugzuCYes3tjeN9O46c3o_JD5LqvP4pqdJ1LjMGLANrsz7TYmvidvu3Tgh-fzhNx_vvpRX-eLb19u6vkit5wCzZuuaTrBTcWoLaXCAirKIS2tqmTDWl411pjWCNGWDS861RqGUjLaCis627ETcr7LXZper4NbmbDR3jh9PV_o7Q7KUgFXxRNN9mxn18E_ThhHvXLRYt-bAf0UdcGAiRJExRM9fUUf_BSG9JOkOEApORNJzXbKBh9jwG7_Agp6W47elqP35aQLn55jp2aF7Z7_ayMBtQM_XY-b_8Tp-debq5fwvz4WnY8</recordid><startdate>20200210</startdate><enddate>20200210</enddate><creator>Ernouf, Guillaume</creator><creator>Chirkin, Egor</creator><creator>Rhyman, Lydia</creator><creator>Ramasami, Ponnadurai</creator><creator>Cintrat, Jean‐Christophe</creator><general>Wiley Subscription Services, Inc</general><general>Wiley-VCH Verlag</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0001-5758-8077</orcidid><orcidid>https://orcid.org/0000-0001-9279-6365</orcidid></search><sort><creationdate>20200210</creationdate><title>Photochemical Strain‐Release‐Driven Cyclobutylation of C(sp3)‐Centered Radicals</title><author>Ernouf, Guillaume ; Chirkin, Egor ; Rhyman, Lydia ; Ramasami, Ponnadurai ; Cintrat, Jean‐Christophe</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5101-bfbbf75a631c489e206150fbbc968b3d56bcaada77d4b52f9da3e8831d7c7fcf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>bicyclo[1.1.0]butanes</topic><topic>Butane</topic><topic>Butanes</topic><topic>Carboxylic acids</topic><topic>Chemical Sciences</topic><topic>cyclobutanes</topic><topic>late-stage functionalization</topic><topic>photocatalysis</topic><topic>Photochemicals</topic><topic>Radicals</topic><topic>strained molecules</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ernouf, Guillaume</creatorcontrib><creatorcontrib>Chirkin, Egor</creatorcontrib><creatorcontrib>Rhyman, Lydia</creatorcontrib><creatorcontrib>Ramasami, Ponnadurai</creatorcontrib><creatorcontrib>Cintrat, Jean‐Christophe</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ernouf, Guillaume</au><au>Chirkin, Egor</au><au>Rhyman, Lydia</au><au>Ramasami, Ponnadurai</au><au>Cintrat, Jean‐Christophe</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photochemical Strain‐Release‐Driven Cyclobutylation of C(sp3)‐Centered Radicals</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2020-02-10</date><risdate>2020</risdate><volume>59</volume><issue>7</issue><spage>2618</spage><epage>2622</epage><pages>2618-2622</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A new photoredox‐catalyzed decarboxylative radical addition approach to functionalized cyclobutanes is described. The reaction involves an unprecedented formal Giese‐type addition of C(sp3)‐centered radicals to highly strained bicyclo[1.1.0]butanes. The mild photoredox conditions, which make use of a readily available and bench stable phenyl sulfonyl bicyclo[1.1.0]butane, proved to be amenable to a diverse range of α‐amino and α‐oxy carboxylic acids, providing a concise route to 1,3‐disubstituted cyclobutanes. Furthermore, kinetic studies and DFT calculations unveiled mechanistic details on bicyclo[1.1.0]butane reactivity relative to the corresponding olefin system.
High‐lying SOMO radicals, generated in situ under visible‐light photoredox conditions, undergo an efficient addition to highly strained bicyclo[1.1.0]butanes, providing a straightforward access to valuable alkylated cyclobutanes.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>31599038</pmid><doi>10.1002/anie.201908951</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-5758-8077</orcidid><orcidid>https://orcid.org/0000-0001-9279-6365</orcidid></addata></record> |
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| subjects | bicyclo[1.1.0]butanes Butane Butanes Carboxylic acids Chemical Sciences cyclobutanes late-stage functionalization photocatalysis Photochemicals Radicals strained molecules |
| title | Photochemical Strain‐Release‐Driven Cyclobutylation of C(sp3)‐Centered Radicals |
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