Transition metal-free direct dehydrogenative arylation of activated C(sp)-H bonds: synthetic ambit and DFT reactivity predictions
A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp 3 )-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses tert -BuOK as the base and nitroarenes as electrophiles to prepare up to gram q...
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| Veröffentlicht in: | Chemical science (Cambridge) 2018-11, Vol.9 (41), p.7992-7999 |
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| container_title | Chemical science (Cambridge) |
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| creator | Lovato, Kaitlyn Guo, Lirong Xu, Qing-Long Liu, Fengting Yousufuddin, Muhammed Ess, Daniel H Kürti, László Gao, Hongyin |
| description | A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp
3
)-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses
tert
-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of α-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states that substrates containing a C(sp
3
)-H bond with a sufficiently low p
K
a
value should readily undergo arylation. The DFT prediction was confirmed through experimental testing of nearly a dozen substrates containing activated C(sp
3
)-H bonds. This arylation method was also used in a one-pot protocol to synthesize over twenty compounds containing all-carbon quaternary centers.
A direct and general mono-arylation of activated C(sp
3
)-H bonds with nitroarenes under transition metal-free conditions has been developed. |
| doi_str_mv | 10.1039/c8sc02758g |
| format | Article |
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3
)-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses
tert
-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of α-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states that substrates containing a C(sp
3
)-H bond with a sufficiently low p
K
a
value should readily undergo arylation. The DFT prediction was confirmed through experimental testing of nearly a dozen substrates containing activated C(sp
3
)-H bonds. This arylation method was also used in a one-pot protocol to synthesize over twenty compounds containing all-carbon quaternary centers.
A direct and general mono-arylation of activated C(sp
3
)-H bonds with nitroarenes under transition metal-free conditions has been developed.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c8sc02758g</identifier><identifier>PMID: 30450183</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Amides ; Bonding ; Crystallography ; Dehydrogenation ; Esters ; Hydrogen bonds ; Nitriles ; Prediction models ; Substrates ; Sulfones ; Transition metals ; X ray spectra</subject><ispartof>Chemical science (Cambridge), 2018-11, Vol.9 (41), p.7992-7999</ispartof><rights>Copyright Royal Society of Chemistry 2018</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c373t-7e8a438ccde06f64b4e2735efe533a8b576c1a4b68d8898ed783e1d1fc8705983</citedby><cites>FETCH-LOGICAL-c373t-7e8a438ccde06f64b4e2735efe533a8b576c1a4b68d8898ed783e1d1fc8705983</cites><orcidid>0000-0002-7520-8362 ; 0000-0002-3412-5894 ; 0000-0003-4450-6866 ; 0000-0003-4049-6832</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,864,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30450183$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lovato, Kaitlyn</creatorcontrib><creatorcontrib>Guo, Lirong</creatorcontrib><creatorcontrib>Xu, Qing-Long</creatorcontrib><creatorcontrib>Liu, Fengting</creatorcontrib><creatorcontrib>Yousufuddin, Muhammed</creatorcontrib><creatorcontrib>Ess, Daniel H</creatorcontrib><creatorcontrib>Kürti, László</creatorcontrib><creatorcontrib>Gao, Hongyin</creatorcontrib><title>Transition metal-free direct dehydrogenative arylation of activated C(sp)-H bonds: synthetic ambit and DFT reactivity predictions</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp
3
)-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses
tert
-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of α-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states that substrates containing a C(sp
3
)-H bond with a sufficiently low p
K
a
value should readily undergo arylation. The DFT prediction was confirmed through experimental testing of nearly a dozen substrates containing activated C(sp
3
)-H bonds. This arylation method was also used in a one-pot protocol to synthesize over twenty compounds containing all-carbon quaternary centers.
A direct and general mono-arylation of activated C(sp
3
)-H bonds with nitroarenes under transition metal-free conditions has been developed.</description><subject>Amides</subject><subject>Bonding</subject><subject>Crystallography</subject><subject>Dehydrogenation</subject><subject>Esters</subject><subject>Hydrogen bonds</subject><subject>Nitriles</subject><subject>Prediction models</subject><subject>Substrates</subject><subject>Sulfones</subject><subject>Transition metals</subject><subject>X ray spectra</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNpd0c9LHDEUB_Aglip2L70rAS-2MDaZN5lkvMm0roLQQ7fnIZO82Y3MjzXJCnv0P2_ctVtoLgnJJ4_H-xLymbNrzqD6ZlQwLJdCLY_Iac4KnpUCquPDOWcnZBbCE0sLgItcfiQnwArBuIJT8rrwegwuummkA0bdZ51HpNZ5NJFaXG2tn5Y46uhekGq_7fXOTh3VJt3piJbWV2H9Jbun7TTacEPDdowrjM5QPbQuUj1a-v1uQT3uvri4pWuP1pm3SuET-dDpPuDsfT8jv-9-LOr77PHn_KG-fcwMSIiZRKULUMZYZGVXFm2BuQSBHQoArVohS8N10ZbKKlUptFIBcss7oyQTlYIzcrWvu_bT8wZDbAYXDPa9HnHahCbnIEqoZCESvfyPPk0bP6buksrT6ISsZFJf98r4KQSPXbP2bkgjajhr3rJpavWr3mUzT_jiveSmHdAe6N8kEjjfAx_M4fVfuPAH63WUEA</recordid><startdate>20181107</startdate><enddate>20181107</enddate><creator>Lovato, Kaitlyn</creator><creator>Guo, Lirong</creator><creator>Xu, Qing-Long</creator><creator>Liu, Fengting</creator><creator>Yousufuddin, Muhammed</creator><creator>Ess, Daniel H</creator><creator>Kürti, László</creator><creator>Gao, Hongyin</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-7520-8362</orcidid><orcidid>https://orcid.org/0000-0002-3412-5894</orcidid><orcidid>https://orcid.org/0000-0003-4450-6866</orcidid><orcidid>https://orcid.org/0000-0003-4049-6832</orcidid></search><sort><creationdate>20181107</creationdate><title>Transition metal-free direct dehydrogenative arylation of activated C(sp)-H bonds: synthetic ambit and DFT reactivity predictions</title><author>Lovato, Kaitlyn ; Guo, Lirong ; Xu, Qing-Long ; Liu, Fengting ; Yousufuddin, Muhammed ; Ess, Daniel H ; Kürti, László ; Gao, Hongyin</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c373t-7e8a438ccde06f64b4e2735efe533a8b576c1a4b68d8898ed783e1d1fc8705983</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Amides</topic><topic>Bonding</topic><topic>Crystallography</topic><topic>Dehydrogenation</topic><topic>Esters</topic><topic>Hydrogen bonds</topic><topic>Nitriles</topic><topic>Prediction models</topic><topic>Substrates</topic><topic>Sulfones</topic><topic>Transition metals</topic><topic>X ray spectra</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lovato, Kaitlyn</creatorcontrib><creatorcontrib>Guo, Lirong</creatorcontrib><creatorcontrib>Xu, Qing-Long</creatorcontrib><creatorcontrib>Liu, Fengting</creatorcontrib><creatorcontrib>Yousufuddin, Muhammed</creatorcontrib><creatorcontrib>Ess, Daniel H</creatorcontrib><creatorcontrib>Kürti, László</creatorcontrib><creatorcontrib>Gao, Hongyin</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lovato, Kaitlyn</au><au>Guo, Lirong</au><au>Xu, Qing-Long</au><au>Liu, Fengting</au><au>Yousufuddin, Muhammed</au><au>Ess, Daniel H</au><au>Kürti, László</au><au>Gao, Hongyin</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Transition metal-free direct dehydrogenative arylation of activated C(sp)-H bonds: synthetic ambit and DFT reactivity predictions</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2018-11-07</date><risdate>2018</risdate><volume>9</volume><issue>41</issue><spage>7992</spage><epage>7999</epage><pages>7992-7999</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp
3
)-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses
tert
-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of α-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states that substrates containing a C(sp
3
)-H bond with a sufficiently low p
K
a
value should readily undergo arylation. The DFT prediction was confirmed through experimental testing of nearly a dozen substrates containing activated C(sp
3
)-H bonds. This arylation method was also used in a one-pot protocol to synthesize over twenty compounds containing all-carbon quaternary centers.
A direct and general mono-arylation of activated C(sp
3
)-H bonds with nitroarenes under transition metal-free conditions has been developed.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>30450183</pmid><doi>10.1039/c8sc02758g</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-7520-8362</orcidid><orcidid>https://orcid.org/0000-0002-3412-5894</orcidid><orcidid>https://orcid.org/0000-0003-4450-6866</orcidid><orcidid>https://orcid.org/0000-0003-4049-6832</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
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| ispartof | Chemical science (Cambridge), 2018-11, Vol.9 (41), p.7992-7999 |
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| language | eng |
| recordid | cdi_pubmed_primary_30450183 |
| source | DOAJ Directory of Open Access Journals; PubMed Central Open Access; EZB-FREE-00999 freely available EZB journals; PubMed Central |
| subjects | Amides Bonding Crystallography Dehydrogenation Esters Hydrogen bonds Nitriles Prediction models Substrates Sulfones Transition metals X ray spectra |
| title | Transition metal-free direct dehydrogenative arylation of activated C(sp)-H bonds: synthetic ambit and DFT reactivity predictions |
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