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Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations
Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramo...
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| Published in: | Science (American Association for the Advancement of Science) 2018-07, Vol.361 (6400), p.381-387 |
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| Main Authors: | , , , , , , , |
| Format: | Article |
| Language: | English |
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| cited_by | cdi_FETCH-LOGICAL-c524t-73d4145899321b7eec6ceec493ed69d60409db2008fb3e9a8bd3a09b353a3be43 |
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| cites | cdi_FETCH-LOGICAL-c524t-73d4145899321b7eec6ceec493ed69d60409db2008fb3e9a8bd3a09b353a3be43 |
| container_end_page | 387 |
| container_issue | 6400 |
| container_start_page | 381 |
| container_title | Science (American Association for the Advancement of Science) |
| container_volume | 361 |
| creator | Popov, Stasik Shao, Brian Bagdasarian, Alex L Benton, Tyler R Zou, Luyi Yang, Zhongyue Houk, K N Nelson, Hosea M |
| description | Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium-weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond-forming reactions, including carbon-hydrogen (C-H) insertion into unactivated sp
C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives. |
| doi_str_mv | 10.1126/science.aat5440 |
| format | article |
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C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.</description><identifier>ISSN: 0036-8075</identifier><identifier>ISSN: 1095-9203</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.aat5440</identifier><identifier>PMID: 30049877</identifier><language>eng</language><publisher>United States: The American Association for the Advancement of Science</publisher><subject>Alkanes ; Anions ; Aromatic compounds ; Bifurcations ; Carbon ; Catalysis ; Cations ; Chemical synthesis ; Chemistry ; Computer applications ; Friedel-Crafts reaction ; Hydrocarbons ; Insertion ; Intermediates ; Organic chemistry ; Silicon ; Solvolysis ; Substitution reactions</subject><ispartof>Science (American Association for the Advancement of Science), 2018-07, Vol.361 (6400), p.381-387</ispartof><rights>Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.</rights><rights>Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c524t-73d4145899321b7eec6ceec493ed69d60409db2008fb3e9a8bd3a09b353a3be43</citedby><cites>FETCH-LOGICAL-c524t-73d4145899321b7eec6ceec493ed69d60409db2008fb3e9a8bd3a09b353a3be43</cites><orcidid>0000-0002-4259-9803 ; 0000-0002-2875-5283 ; 0000-0002-8870-0807 ; 0000-0002-8387-5261 ; 0000-0002-4666-2793 ; 0000-0003-2281-8068</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,2882,2883,27923,27924</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30049877$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Popov, Stasik</creatorcontrib><creatorcontrib>Shao, Brian</creatorcontrib><creatorcontrib>Bagdasarian, Alex L</creatorcontrib><creatorcontrib>Benton, Tyler R</creatorcontrib><creatorcontrib>Zou, Luyi</creatorcontrib><creatorcontrib>Yang, Zhongyue</creatorcontrib><creatorcontrib>Houk, K N</creatorcontrib><creatorcontrib>Nelson, Hosea M</creatorcontrib><title>Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations</title><title>Science (American Association for the Advancement of Science)</title><addtitle>Science</addtitle><description>Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium-weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond-forming reactions, including carbon-hydrogen (C-H) insertion into unactivated sp
C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.</description><subject>Alkanes</subject><subject>Anions</subject><subject>Aromatic compounds</subject><subject>Bifurcations</subject><subject>Carbon</subject><subject>Catalysis</subject><subject>Cations</subject><subject>Chemical synthesis</subject><subject>Chemistry</subject><subject>Computer applications</subject><subject>Friedel-Crafts reaction</subject><subject>Hydrocarbons</subject><subject>Insertion</subject><subject>Intermediates</subject><subject>Organic chemistry</subject><subject>Silicon</subject><subject>Solvolysis</subject><subject>Substitution reactions</subject><issn>0036-8075</issn><issn>1095-9203</issn><issn>1095-9203</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNpdkU1LxDAQhoMoun6cvUnAi5e60yZNEw-CLH6B4GU9hzSd1Wg30aRd8d_bdVdRL5nAPPMww0vIYQ6neV6IcbIOvcVTY7qSc9ggoxxUmakC2CYZATCRSajKHbKb0jPA0FNsm-wwAK5kVY2InqKxT84_UuNpaBtqTayDNZ0Lnnp8p1109iWd0VvfYZyHFm3fmkgn2Q11PmH8AuMgWX4SDTO6cP6jpStF2idbM9MmPFjXPfJwdTmd3GR399e3k4u7zJYF77KKNTznpVSKFXldIVphh4crho1QjQAOqqkLADmrGSoj64YZUDUrmWE1crZHzlfe176eY2PRd9G0-jW6uYkfOhin_3a8e9KPYaGFkFIUYhCcrAUxvPWYOj13yWLbGo-hT7qASpayKEU1oMf_0OfQRz-ct6SEEiDVUjheUTaGlCLOfpbJQS_D0-vw9Dq8YeLo9w0__Hda7BPGFpmK</recordid><startdate>20180727</startdate><enddate>20180727</enddate><creator>Popov, Stasik</creator><creator>Shao, Brian</creator><creator>Bagdasarian, Alex L</creator><creator>Benton, Tyler R</creator><creator>Zou, Luyi</creator><creator>Yang, Zhongyue</creator><creator>Houk, K N</creator><creator>Nelson, Hosea M</creator><general>The American Association for the Advancement of Science</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QG</scope><scope>7QL</scope><scope>7QP</scope><scope>7QQ</scope><scope>7QR</scope><scope>7SC</scope><scope>7SE</scope><scope>7SN</scope><scope>7SP</scope><scope>7SR</scope><scope>7SS</scope><scope>7T7</scope><scope>7TA</scope><scope>7TB</scope><scope>7TK</scope><scope>7TM</scope><scope>7U5</scope><scope>7U9</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>H94</scope><scope>JG9</scope><scope>JQ2</scope><scope>K9.</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>M7N</scope><scope>P64</scope><scope>RC3</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-4259-9803</orcidid><orcidid>https://orcid.org/0000-0002-2875-5283</orcidid><orcidid>https://orcid.org/0000-0002-8870-0807</orcidid><orcidid>https://orcid.org/0000-0002-8387-5261</orcidid><orcidid>https://orcid.org/0000-0002-4666-2793</orcidid><orcidid>https://orcid.org/0000-0003-2281-8068</orcidid></search><sort><creationdate>20180727</creationdate><title>Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations</title><author>Popov, Stasik ; 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C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.</abstract><cop>United States</cop><pub>The American Association for the Advancement of Science</pub><pmid>30049877</pmid><doi>10.1126/science.aat5440</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-4259-9803</orcidid><orcidid>https://orcid.org/0000-0002-2875-5283</orcidid><orcidid>https://orcid.org/0000-0002-8870-0807</orcidid><orcidid>https://orcid.org/0000-0002-8387-5261</orcidid><orcidid>https://orcid.org/0000-0002-4666-2793</orcidid><orcidid>https://orcid.org/0000-0003-2281-8068</orcidid><oa>free_for_read</oa></addata></record> |
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| identifier | ISSN: 0036-8075 |
| ispartof | Science (American Association for the Advancement of Science), 2018-07, Vol.361 (6400), p.381-387 |
| issn | 0036-8075 1095-9203 1095-9203 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_6688626 |
| source | Science Magazine; Alma/SFX Local Collection |
| subjects | Alkanes Anions Aromatic compounds Bifurcations Carbon Catalysis Cations Chemical synthesis Chemistry Computer applications Friedel-Crafts reaction Hydrocarbons Insertion Intermediates Organic chemistry Silicon Solvolysis Substitution reactions |
| title | Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations |
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