Photoredox‐Coupled F‐Nucleophilic Addition: Allylation of gem‐Difluoroalkenes
A novel strategy for the expedient construction of CF3‐embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single‐electron oxidation, electron‐rich gem‐difluoroalkenes, which otherwise are essentially reluctant towards F‐nucl...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2019-03, Vol.58 (12), p.3918-3922 |
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| creator | Liu, Haidong Ge, Liang Wang, Ding‐Xing Chen, Nan Feng, Chao |
| description | A novel strategy for the expedient construction of CF3‐embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single‐electron oxidation, electron‐rich gem‐difluoroalkenes, which otherwise are essentially reluctant towards F‐nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of α‐CF3‐substituted benzylic radical intermediates using cheap and readily available starting materials.
Finding a gem: The fluoroallylation of gem‐difluoroalkenes with inexpensive Et3N⋅3 HF and readily available allylsulfone has been developed. The photoredox‐coupled fluoride nucleophilic addition process, combined with the radical allylation allows expedient access to a large collection of functionalized homoallylic trifluoromethane derivatives under mild visible‐light‐induced conditions at room temperature. |
| doi_str_mv | 10.1002/anie.201814308 |
| format | Article |
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Finding a gem: The fluoroallylation of gem‐difluoroalkenes with inexpensive Et3N⋅3 HF and readily available allylsulfone has been developed. The photoredox‐coupled fluoride nucleophilic addition process, combined with the radical allylation allows expedient access to a large collection of functionalized homoallylic trifluoromethane derivatives under mild visible‐light‐induced conditions at room temperature.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201814308</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Allyl compounds ; allylic compounds ; Catalysis ; Chemical reactions ; fluorine ; Intermediates ; Oxidation ; photochemistry ; Photoredox catalysis ; radicals ; reaction mechanisms</subject><ispartof>Angewandte Chemie International Edition, 2019-03, Vol.58 (12), p.3918-3922</ispartof><rights>2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4538-d4bc787ca1dbe988236d1d95f48fae74b2fe784cde2f95569f7b1d200356efb53</citedby><cites>FETCH-LOGICAL-c4538-d4bc787ca1dbe988236d1d95f48fae74b2fe784cde2f95569f7b1d200356efb53</cites><orcidid>0000-0003-4494-6845</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.201814308$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201814308$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids></links><search><creatorcontrib>Liu, Haidong</creatorcontrib><creatorcontrib>Ge, Liang</creatorcontrib><creatorcontrib>Wang, Ding‐Xing</creatorcontrib><creatorcontrib>Chen, Nan</creatorcontrib><creatorcontrib>Feng, Chao</creatorcontrib><title>Photoredox‐Coupled F‐Nucleophilic Addition: Allylation of gem‐Difluoroalkenes</title><title>Angewandte Chemie International Edition</title><description>A novel strategy for the expedient construction of CF3‐embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single‐electron oxidation, electron‐rich gem‐difluoroalkenes, which otherwise are essentially reluctant towards F‐nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of α‐CF3‐substituted benzylic radical intermediates using cheap and readily available starting materials.
Finding a gem: The fluoroallylation of gem‐difluoroalkenes with inexpensive Et3N⋅3 HF and readily available allylsulfone has been developed. The photoredox‐coupled fluoride nucleophilic addition process, combined with the radical allylation allows expedient access to a large collection of functionalized homoallylic trifluoromethane derivatives under mild visible‐light‐induced conditions at room temperature.</description><subject>Allyl compounds</subject><subject>allylic compounds</subject><subject>Catalysis</subject><subject>Chemical reactions</subject><subject>fluorine</subject><subject>Intermediates</subject><subject>Oxidation</subject><subject>photochemistry</subject><subject>Photoredox catalysis</subject><subject>radicals</subject><subject>reaction mechanisms</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqF0LtOwzAYBeAIgUQprMyRWFhSfEtss0WlhUpVQQLmKIl_Uxc3LnEj6MYj8Iw8Ca6KQGJh8hm-Y9knik4xGmCEyEXZGBgQhAVmFIm9qIdTghPKOd0PmVGacJHiw-jI-0XwQqCsF93fzd3ataDc2-f7x9B1KwsqHoc862oLbjU31tRxrpRZG9dcxrm1G1tuc-x0_ATLQK-Mtp1rXWmfoQF_HB3o0no4-T770eN49DC8Saa315NhPk1qllKRKFbVXPC6xKoCKQShmcJKppoJXQJnFdHABasVEC3TNJOaV1gRhGiaga5S2o_Od_euWvfSgV8XS-NrsLZswHW-IJjL8G3JWaBnf-jCdW0TXheURBQzQmVQg52qW-d9C7pYtWZZtpsCo2K7cbHduPjZOBTkrvBqLGz-0UU-m4x-u1_qIIOZ</recordid><startdate>20190318</startdate><enddate>20190318</enddate><creator>Liu, Haidong</creator><creator>Ge, Liang</creator><creator>Wang, Ding‐Xing</creator><creator>Chen, Nan</creator><creator>Feng, Chao</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-4494-6845</orcidid></search><sort><creationdate>20190318</creationdate><title>Photoredox‐Coupled F‐Nucleophilic Addition: Allylation of gem‐Difluoroalkenes</title><author>Liu, Haidong ; Ge, Liang ; Wang, Ding‐Xing ; Chen, Nan ; Feng, Chao</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4538-d4bc787ca1dbe988236d1d95f48fae74b2fe784cde2f95569f7b1d200356efb53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Allyl compounds</topic><topic>allylic compounds</topic><topic>Catalysis</topic><topic>Chemical reactions</topic><topic>fluorine</topic><topic>Intermediates</topic><topic>Oxidation</topic><topic>photochemistry</topic><topic>Photoredox catalysis</topic><topic>radicals</topic><topic>reaction mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Haidong</creatorcontrib><creatorcontrib>Ge, Liang</creatorcontrib><creatorcontrib>Wang, Ding‐Xing</creatorcontrib><creatorcontrib>Chen, Nan</creatorcontrib><creatorcontrib>Feng, Chao</creatorcontrib><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liu, Haidong</au><au>Ge, Liang</au><au>Wang, Ding‐Xing</au><au>Chen, Nan</au><au>Feng, Chao</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photoredox‐Coupled F‐Nucleophilic Addition: Allylation of gem‐Difluoroalkenes</atitle><jtitle>Angewandte Chemie International Edition</jtitle><date>2019-03-18</date><risdate>2019</risdate><volume>58</volume><issue>12</issue><spage>3918</spage><epage>3922</epage><pages>3918-3922</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A novel strategy for the expedient construction of CF3‐embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single‐electron oxidation, electron‐rich gem‐difluoroalkenes, which otherwise are essentially reluctant towards F‐nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of α‐CF3‐substituted benzylic radical intermediates using cheap and readily available starting materials.
Finding a gem: The fluoroallylation of gem‐difluoroalkenes with inexpensive Et3N⋅3 HF and readily available allylsulfone has been developed. The photoredox‐coupled fluoride nucleophilic addition process, combined with the radical allylation allows expedient access to a large collection of functionalized homoallylic trifluoromethane derivatives under mild visible‐light‐induced conditions at room temperature.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/anie.201814308</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0003-4494-6845</orcidid></addata></record> |
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| identifier | ISSN: 1433-7851 |
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| language | eng |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Allyl compounds allylic compounds Catalysis Chemical reactions fluorine Intermediates Oxidation photochemistry Photoredox catalysis radicals reaction mechanisms |
| title | Photoredox‐Coupled F‐Nucleophilic Addition: Allylation of gem‐Difluoroalkenes |
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