Photoredox Generation of Carbon‐Centered Radicals Enables the Construction of 1,1‐Difluoroalkene Carbonyl Mimics
Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Using visible‐light‐activated catalysts in conjunction with an arsenal of carbon‐radical precursors, an array of trifluoromethyl‐substituted alkenes undergoes radical defluorinative alkylation. Nonstabilized p...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2017-11, Vol.56 (47), p.15073-15077 |
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| container_title | Angewandte Chemie International Edition |
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| creator | Lang, Simon B. Wiles, Rebecca J. Kelly, Christopher B. Molander, Gary A. |
| description | Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Using visible‐light‐activated catalysts in conjunction with an arsenal of carbon‐radical precursors, an array of trifluoromethyl‐substituted alkenes undergoes radical defluorinative alkylation. Nonstabilized primary, secondary, and tertiary radicals can be used to install functional groups in a convergent manner, which would otherwise be challenging by two‐electron pathways. The process readily extends to other perfluoroalkyl‐substituted alkenes. In addition, we report the development of an organotrifluoroborate reagent to expedite the synthesis of the requisite trifluoromethyl‐substituted alkene starting materials.
CF3 today, CF2 tomorrow: Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Trifluoromethyl‐substituted alkenes readily undergo radical defluorinative alkylation using visible‐light‐activated catalysts and an arsenal of C‐radical precursors. Nonstabilized primary, secondary, and tertiary radicals can be used to install various functional groups. PC=photocatalyst. |
| doi_str_mv | 10.1002/anie.201709487 |
| format | Article |
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CF3 today, CF2 tomorrow: Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Trifluoromethyl‐substituted alkenes readily undergo radical defluorinative alkylation using visible‐light‐activated catalysts and an arsenal of C‐radical precursors. Nonstabilized primary, secondary, and tertiary radicals can be used to install various functional groups. PC=photocatalyst.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201709487</identifier><identifier>PMID: 28960656</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Activated carbon ; Alkenes ; Alkenes - chemical synthesis ; Alkenes - chemistry ; Alkylation ; Boron Compounds - chemistry ; Carbon - chemistry ; Carbonyls ; Catalysts ; Fluorenes - chemistry ; fluorine ; Functional groups ; Indicators and Reagents - chemistry ; Molecular Mimicry ; Oxidation-Reduction ; Photochemical Processes ; photochemistry ; Radicals ; Stereoisomerism</subject><ispartof>Angewandte Chemie International Edition, 2017-11, Vol.56 (47), p.15073-15077</ispartof><rights>2017 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5167-7249d097a293413a2e4dd3c548180d4ad19918fd04ad0a82e45165023ec685333</citedby><cites>FETCH-LOGICAL-c5167-7249d097a293413a2e4dd3c548180d4ad19918fd04ad0a82e45165023ec685333</cites><orcidid>0000-0001-5380-2996 ; 0000-0002-5530-8606 ; 0000-0002-0467-9335 ; 0000-0002-9114-5584</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201709487$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201709487$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,777,781,1412,27905,27906,45555,45556</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28960656$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lang, Simon B.</creatorcontrib><creatorcontrib>Wiles, Rebecca J.</creatorcontrib><creatorcontrib>Kelly, Christopher B.</creatorcontrib><creatorcontrib>Molander, Gary A.</creatorcontrib><title>Photoredox Generation of Carbon‐Centered Radicals Enables the Construction of 1,1‐Difluoroalkene Carbonyl Mimics</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Using visible‐light‐activated catalysts in conjunction with an arsenal of carbon‐radical precursors, an array of trifluoromethyl‐substituted alkenes undergoes radical defluorinative alkylation. Nonstabilized primary, secondary, and tertiary radicals can be used to install functional groups in a convergent manner, which would otherwise be challenging by two‐electron pathways. The process readily extends to other perfluoroalkyl‐substituted alkenes. In addition, we report the development of an organotrifluoroborate reagent to expedite the synthesis of the requisite trifluoromethyl‐substituted alkene starting materials.
CF3 today, CF2 tomorrow: Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Trifluoromethyl‐substituted alkenes readily undergo radical defluorinative alkylation using visible‐light‐activated catalysts and an arsenal of C‐radical precursors. Nonstabilized primary, secondary, and tertiary radicals can be used to install various functional groups. PC=photocatalyst.</description><subject>Activated carbon</subject><subject>Alkenes</subject><subject>Alkenes - chemical synthesis</subject><subject>Alkenes - chemistry</subject><subject>Alkylation</subject><subject>Boron Compounds - chemistry</subject><subject>Carbon - chemistry</subject><subject>Carbonyls</subject><subject>Catalysts</subject><subject>Fluorenes - chemistry</subject><subject>fluorine</subject><subject>Functional groups</subject><subject>Indicators and Reagents - chemistry</subject><subject>Molecular Mimicry</subject><subject>Oxidation-Reduction</subject><subject>Photochemical Processes</subject><subject>photochemistry</subject><subject>Radicals</subject><subject>Stereoisomerism</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkMtOwzAQRS0EoqWwZYkssSXFjhM_llUopVJ5CME6cmNHdUnjYieC7vgEvpEvwVUfLFnNSHPuGekCcI5RHyMUX8va6H6MMEMi4ewAdHEa44gwRg7DnhASMZ7iDjjxfh54zhE9Bp2YC4poSrugeZrZxjqt7Ccc6Vo72RhbQ1vCTLqprX--vjNdNzoQ8FkqU8jKw2Etp5X2sJlpmNnaN64tdjF8hUPmxpRVa52V1VuQbl2rCt6bhSn8KTgqg0efbWcPvN4OX7K7aPI4GmeDSVSkmLKIxYlQSDAZC5JgImOdKEWKNOGYI5VIhYXAvFQorEjycA6xFMVEF5SnhJAeuNx4l86-t9o3-dy2rg4vcywo4ZTjlAWqv6EKZ713usyXziykW-UY5euS83XJ-b7kELjYatvpQqs9vms1AGIDfJhKr_7R5YOH8fBP_gvtF4pX</recordid><startdate>20171120</startdate><enddate>20171120</enddate><creator>Lang, Simon B.</creator><creator>Wiles, Rebecca J.</creator><creator>Kelly, Christopher B.</creator><creator>Molander, Gary A.</creator><general>Wiley Subscription Services, Inc</general><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>7TM</scope><scope>K9.</scope><orcidid>https://orcid.org/0000-0001-5380-2996</orcidid><orcidid>https://orcid.org/0000-0002-5530-8606</orcidid><orcidid>https://orcid.org/0000-0002-0467-9335</orcidid><orcidid>https://orcid.org/0000-0002-9114-5584</orcidid></search><sort><creationdate>20171120</creationdate><title>Photoredox Generation of Carbon‐Centered Radicals Enables the Construction of 1,1‐Difluoroalkene Carbonyl Mimics</title><author>Lang, Simon B. ; Wiles, Rebecca J. ; Kelly, Christopher B. ; Molander, Gary A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5167-7249d097a293413a2e4dd3c548180d4ad19918fd04ad0a82e45165023ec685333</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Activated carbon</topic><topic>Alkenes</topic><topic>Alkenes - chemical synthesis</topic><topic>Alkenes - chemistry</topic><topic>Alkylation</topic><topic>Boron Compounds - chemistry</topic><topic>Carbon - chemistry</topic><topic>Carbonyls</topic><topic>Catalysts</topic><topic>Fluorenes - chemistry</topic><topic>fluorine</topic><topic>Functional groups</topic><topic>Indicators and Reagents - chemistry</topic><topic>Molecular Mimicry</topic><topic>Oxidation-Reduction</topic><topic>Photochemical Processes</topic><topic>photochemistry</topic><topic>Radicals</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lang, Simon B.</creatorcontrib><creatorcontrib>Wiles, Rebecca J.</creatorcontrib><creatorcontrib>Kelly, Christopher B.</creatorcontrib><creatorcontrib>Molander, Gary A.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lang, Simon B.</au><au>Wiles, Rebecca J.</au><au>Kelly, Christopher B.</au><au>Molander, Gary A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photoredox Generation of Carbon‐Centered Radicals Enables the Construction of 1,1‐Difluoroalkene Carbonyl Mimics</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2017-11-20</date><risdate>2017</risdate><volume>56</volume><issue>47</issue><spage>15073</spage><epage>15077</epage><pages>15073-15077</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Using visible‐light‐activated catalysts in conjunction with an arsenal of carbon‐radical precursors, an array of trifluoromethyl‐substituted alkenes undergoes radical defluorinative alkylation. Nonstabilized primary, secondary, and tertiary radicals can be used to install functional groups in a convergent manner, which would otherwise be challenging by two‐electron pathways. The process readily extends to other perfluoroalkyl‐substituted alkenes. In addition, we report the development of an organotrifluoroborate reagent to expedite the synthesis of the requisite trifluoromethyl‐substituted alkene starting materials.
CF3 today, CF2 tomorrow: Described is a facile, scalable route to access functional‐group‐rich gem‐difluoroalkenes. Trifluoromethyl‐substituted alkenes readily undergo radical defluorinative alkylation using visible‐light‐activated catalysts and an arsenal of C‐radical precursors. Nonstabilized primary, secondary, and tertiary radicals can be used to install various functional groups. PC=photocatalyst.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>28960656</pmid><doi>10.1002/anie.201709487</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-5380-2996</orcidid><orcidid>https://orcid.org/0000-0002-5530-8606</orcidid><orcidid>https://orcid.org/0000-0002-0467-9335</orcidid><orcidid>https://orcid.org/0000-0002-9114-5584</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Activated carbon Alkenes Alkenes - chemical synthesis Alkenes - chemistry Alkylation Boron Compounds - chemistry Carbon - chemistry Carbonyls Catalysts Fluorenes - chemistry fluorine Functional groups Indicators and Reagents - chemistry Molecular Mimicry Oxidation-Reduction Photochemical Processes photochemistry Radicals Stereoisomerism |
| title | Photoredox Generation of Carbon‐Centered Radicals Enables the Construction of 1,1‐Difluoroalkene Carbonyl Mimics |
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