Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity
A highly chemoselective phenol cross-coupling reaction catalyzed by a Cr-salen catalyst was developed. Kinetic studies showed that the oxidation of Cr(III) to Cr(V) is the rate-determining step of the reaction. In addition, experimental stoichiometric analysis showed that a high valent Cr(V) spec...
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| Veröffentlicht in: | Journal of the American Chemical Society 2019-06, Vol.141 (25), p.10016-10032 |
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| container_title | Journal of the American Chemical Society |
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| creator | Nieves-Quinones, Yexenia Paniak, Thomas J Lee, Young Eun Kim, Sun Min Tcyrulnikov, Sergei Kozlowski, Marisa C |
| description | A highly chemoselective phenol cross-coupling reaction catalyzed by a Cr-salen catalyst was developed. Kinetic studies showed that the oxidation of Cr(III) to Cr(V) is the rate-determining step of the reaction. In addition, experimental stoichiometric analysis showed that a high valent Cr(V) species is the active catalyst for this process. The selectivity of the reaction was found to be determined by the cross-coupling carbon–carbon bond forming reaction, rather than any precoordination species. It appears that the lowest energy cross-coupling pathway requires a lesser degree of electronic reorganization in its transition state vs the lowest energy homocoupling pathway. This result was supported by stoichiometric Cr(V) kinetics, 13C kinetic isotope effects, and density functional theory (DFT) calculations. The understanding of the full landscape of this reaction allowed us to develop a general analysis to predict the regioselectivity of the cross-coupling reaction. |
| doi_str_mv | 10.1021/jacs.9b03890 |
| format | Article |
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Am. Chem. Soc</addtitle><description>A highly chemoselective phenol cross-coupling reaction catalyzed by a Cr-salen catalyst was developed. Kinetic studies showed that the oxidation of Cr(III) to Cr(V) is the rate-determining step of the reaction. In addition, experimental stoichiometric analysis showed that a high valent Cr(V) species is the active catalyst for this process. The selectivity of the reaction was found to be determined by the cross-coupling carbon–carbon bond forming reaction, rather than any precoordination species. It appears that the lowest energy cross-coupling pathway requires a lesser degree of electronic reorganization in its transition state vs the lowest energy homocoupling pathway. This result was supported by stoichiometric Cr(V) kinetics, 13C kinetic isotope effects, and density functional theory (DFT) calculations. The understanding of the full landscape of this reaction allowed us to develop a general analysis to predict the regioselectivity of the cross-coupling reaction.</description><subject>carbon</subject><subject>catalysts</subject><subject>catalytic activity</subject><subject>chemical bonding</subject><subject>chemoselectivity</subject><subject>chromium</subject><subject>cross-coupling reactions</subject><subject>density functional theory</subject><subject>energy</subject><subject>landscapes</subject><subject>oxidation</subject><subject>phenol</subject><subject>regioselectivity</subject><subject>stable isotopes</subject><issn>0002-7863</issn><issn>1520-5126</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqFkU1v1DAQhi0EokvhxhnlyIEUj53EDgckFPEltSpS4cTBcpLxxivHXuyk0vLrSdSlLRJST6PRPPPOx0vIS6BnQBm83ekundUt5bKmj8gGSkbzElj1mGwopSwXsuIn5FlKuyUtmISn5IQDsJIB3ZCfzRDDaOcxv9IOfdboSbvDb-yzJoaU8ibMe2f9Ngsm-zagDy69yy6wG7S3acy077PLaLfWr8A0YHaFDrvJXtvp8Jw8MdolfHGMp-THp4_fmy_5-eXnr82H81yXJZ9yY1C3ZWcATN0zgzVK3gpsK953fSEFh7JEQRELKvmS9W1toBA9Y0xXBZf8lLy_0d3P7Yh9h36K2ql9tKOOBxW0Vf9WvB3UNlyrqmKSVbAIvD4KxPBrxjSp0aYOndMew5wU47QEKYTgD6OMMwCglVjQNzdot34yorndCKharVOrdepo3YK_un_FLfzXq7vRa9cuzNEvT_2_1h_7-6MO</recordid><startdate>20190626</startdate><enddate>20190626</enddate><creator>Nieves-Quinones, Yexenia</creator><creator>Paniak, Thomas J</creator><creator>Lee, Young Eun</creator><creator>Kim, Sun Min</creator><creator>Tcyrulnikov, Sergei</creator><creator>Kozlowski, Marisa C</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7S9</scope><scope>L.6</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-4225-7125</orcidid></search><sort><creationdate>20190626</creationdate><title>Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity</title><author>Nieves-Quinones, Yexenia ; Paniak, Thomas J ; Lee, Young Eun ; Kim, Sun Min ; Tcyrulnikov, Sergei ; Kozlowski, Marisa C</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a553t-ffeab5cf11f9d2fe9e83b7eb63dcd4873155e70ee4083731db9f147d222a64383</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>carbon</topic><topic>catalysts</topic><topic>catalytic activity</topic><topic>chemical bonding</topic><topic>chemoselectivity</topic><topic>chromium</topic><topic>cross-coupling reactions</topic><topic>density functional theory</topic><topic>energy</topic><topic>landscapes</topic><topic>oxidation</topic><topic>phenol</topic><topic>regioselectivity</topic><topic>stable isotopes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Nieves-Quinones, Yexenia</creatorcontrib><creatorcontrib>Paniak, Thomas J</creatorcontrib><creatorcontrib>Lee, Young Eun</creatorcontrib><creatorcontrib>Kim, Sun Min</creatorcontrib><creatorcontrib>Tcyrulnikov, Sergei</creatorcontrib><creatorcontrib>Kozlowski, Marisa C</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Nieves-Quinones, Yexenia</au><au>Paniak, Thomas J</au><au>Lee, Young Eun</au><au>Kim, Sun Min</au><au>Tcyrulnikov, Sergei</au><au>Kozlowski, Marisa C</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2019-06-26</date><risdate>2019</risdate><volume>141</volume><issue>25</issue><spage>10016</spage><epage>10032</epage><pages>10016-10032</pages><issn>0002-7863</issn><issn>1520-5126</issn><eissn>1520-5126</eissn><abstract>A highly chemoselective phenol cross-coupling reaction catalyzed by a Cr-salen catalyst was developed. Kinetic studies showed that the oxidation of Cr(III) to Cr(V) is the rate-determining step of the reaction. In addition, experimental stoichiometric analysis showed that a high valent Cr(V) species is the active catalyst for this process. The selectivity of the reaction was found to be determined by the cross-coupling carbon–carbon bond forming reaction, rather than any precoordination species. It appears that the lowest energy cross-coupling pathway requires a lesser degree of electronic reorganization in its transition state vs the lowest energy homocoupling pathway. 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| source | ACS Publications |
| subjects | carbon catalysts catalytic activity chemical bonding chemoselectivity chromium cross-coupling reactions density functional theory energy landscapes oxidation phenol regioselectivity stable isotopes |
| title | Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity |
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