Intermediates and mechanism in iron-catalyzed C-H methylation with trimethylaluminum
A mechanistic study is performed on the reaction method for iron-catalyzed C-H methylation with AlMe 3 reagent, previously proposed to involve cyclometalated iron( iii ) intermediates and an iron( iii )/( i ) reaction cycle. Detailed spectroscopic studies ( 57 Fe Mössbauer, EPR) during catalysis and...
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| Veröffentlicht in: | Chemical communications (Cambridge, England) England), 2021-11, Vol.57 (95), p.12784-12787 |
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| container_title | Chemical communications (Cambridge, England) |
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| creator | Bhatia, Shilpa DeMuth, Joshua C Neidig, Michael L |
| description | A mechanistic study is performed on the reaction method for iron-catalyzed C-H methylation with AlMe
3
reagent, previously proposed to involve cyclometalated iron(
iii
) intermediates and an iron(
iii
)/(
i
) reaction cycle. Detailed spectroscopic studies (
57
Fe Mössbauer, EPR) during catalysis and in stoichiometric reactions identify iron(
ii
) complexes, including cyclometalated iron(
ii
) intermediates, as the major iron species formed
in situ
under catalytic reaction conditions. Reaction studies identify a cyclometalated iron(
ii
)-methyl species as the key intermediate leading to C-H methylated product upon reaction with oxidant, consistent with a previously proposed iron(
ii
)/iron(
iii
)/iron(
i
) reaction manifold for C-H arylation.
Iron-catalyzed C-H methylation with organoaluminum reagents accesses reactive cyclometalated iron(
ii
) intermediates. |
| doi_str_mv | 10.1039/d1cc05607g |
| format | Article |
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3
reagent, previously proposed to involve cyclometalated iron(
iii
) intermediates and an iron(
iii
)/(
i
) reaction cycle. Detailed spectroscopic studies (
57
Fe Mössbauer, EPR) during catalysis and in stoichiometric reactions identify iron(
ii
) complexes, including cyclometalated iron(
ii
) intermediates, as the major iron species formed
in situ
under catalytic reaction conditions. Reaction studies identify a cyclometalated iron(
ii
)-methyl species as the key intermediate leading to C-H methylated product upon reaction with oxidant, consistent with a previously proposed iron(
ii
)/iron(
iii
)/iron(
i
) reaction manifold for C-H arylation.
Iron-catalyzed C-H methylation with organoaluminum reagents accesses reactive cyclometalated iron(
ii
) intermediates.</description><identifier>ISSN: 1359-7345</identifier><identifier>EISSN: 1364-548X</identifier><identifier>DOI: 10.1039/d1cc05607g</identifier><identifier>PMID: 34782896</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Catalysis ; Coordination compounds ; Iron ; Iron 57 ; Methylation ; Oxidizing agents ; Reagents</subject><ispartof>Chemical communications (Cambridge, England), 2021-11, Vol.57 (95), p.12784-12787</ispartof><rights>Copyright Royal Society of Chemistry 2021</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c337t-a01bfbd0eb1e244b643ee0af5593fe3ffcfbbe6ee1aeece9c15098187731a6613</citedby><cites>FETCH-LOGICAL-c337t-a01bfbd0eb1e244b643ee0af5593fe3ffcfbbe6ee1aeece9c15098187731a6613</cites><orcidid>0000-0002-2300-3867</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/34782896$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Bhatia, Shilpa</creatorcontrib><creatorcontrib>DeMuth, Joshua C</creatorcontrib><creatorcontrib>Neidig, Michael L</creatorcontrib><title>Intermediates and mechanism in iron-catalyzed C-H methylation with trimethylaluminum</title><title>Chemical communications (Cambridge, England)</title><addtitle>Chem Commun (Camb)</addtitle><description>A mechanistic study is performed on the reaction method for iron-catalyzed C-H methylation with AlMe
3
reagent, previously proposed to involve cyclometalated iron(
iii
) intermediates and an iron(
iii
)/(
i
) reaction cycle. Detailed spectroscopic studies (
57
Fe Mössbauer, EPR) during catalysis and in stoichiometric reactions identify iron(
ii
) complexes, including cyclometalated iron(
ii
) intermediates, as the major iron species formed
in situ
under catalytic reaction conditions. Reaction studies identify a cyclometalated iron(
ii
)-methyl species as the key intermediate leading to C-H methylated product upon reaction with oxidant, consistent with a previously proposed iron(
ii
)/iron(
iii
)/iron(
i
) reaction manifold for C-H arylation.
Iron-catalyzed C-H methylation with organoaluminum reagents accesses reactive cyclometalated iron(
ii
) intermediates.</description><subject>Catalysis</subject><subject>Coordination compounds</subject><subject>Iron</subject><subject>Iron 57</subject><subject>Methylation</subject><subject>Oxidizing agents</subject><subject>Reagents</subject><issn>1359-7345</issn><issn>1364-548X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpdkd9LwzAQx4MoOqcvvisFX0SoJk3SH49SdRsMfJngW0nTi4u06UxSZP71Zm4qeC933H3uuPseQmcE3xBMi9uGSIl5irPXPTQiNGUxZ_nL_ibmRZxRxo_QsXNvOBjh-SE6oizLk7xIR2gxMx5sB40WHlwkTBN1IJfCaNdF2kTa9iaWwot2_QlNVMbTUPfLdSu87k30of0y8lbvcu3QaTN0J-hAidbB6c6P0fPjw6KcxvOnyay8m8eS0szHApNa1Q2GmkDCWJ0yCoCF4rygCqhSUtU1pABEAEgoJOG4yEmeZZSINCV0jK62c1e2fx_A-arTTkLbCgP94KqEFznOQksR0Mt_6Fs_WBO2q5IUM04znrBAXW8paXvnLKhqFW4Tdl0RXG20ru5JWX5rPQnwxW7kUAcBf9EfcQNwvgWsk7_Vv2fRLzHZhKE</recordid><startdate>20211130</startdate><enddate>20211130</enddate><creator>Bhatia, Shilpa</creator><creator>DeMuth, Joshua C</creator><creator>Neidig, Michael L</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-2300-3867</orcidid></search><sort><creationdate>20211130</creationdate><title>Intermediates and mechanism in iron-catalyzed C-H methylation with trimethylaluminum</title><author>Bhatia, Shilpa ; DeMuth, Joshua C ; Neidig, Michael L</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c337t-a01bfbd0eb1e244b643ee0af5593fe3ffcfbbe6ee1aeece9c15098187731a6613</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Catalysis</topic><topic>Coordination compounds</topic><topic>Iron</topic><topic>Iron 57</topic><topic>Methylation</topic><topic>Oxidizing agents</topic><topic>Reagents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bhatia, Shilpa</creatorcontrib><creatorcontrib>DeMuth, Joshua C</creatorcontrib><creatorcontrib>Neidig, Michael L</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Chemical communications (Cambridge, England)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bhatia, Shilpa</au><au>DeMuth, Joshua C</au><au>Neidig, Michael L</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Intermediates and mechanism in iron-catalyzed C-H methylation with trimethylaluminum</atitle><jtitle>Chemical communications (Cambridge, England)</jtitle><addtitle>Chem Commun (Camb)</addtitle><date>2021-11-30</date><risdate>2021</risdate><volume>57</volume><issue>95</issue><spage>12784</spage><epage>12787</epage><pages>12784-12787</pages><issn>1359-7345</issn><eissn>1364-548X</eissn><abstract>A mechanistic study is performed on the reaction method for iron-catalyzed C-H methylation with AlMe
3
reagent, previously proposed to involve cyclometalated iron(
iii
) intermediates and an iron(
iii
)/(
i
) reaction cycle. Detailed spectroscopic studies (
57
Fe Mössbauer, EPR) during catalysis and in stoichiometric reactions identify iron(
ii
) complexes, including cyclometalated iron(
ii
) intermediates, as the major iron species formed
in situ
under catalytic reaction conditions. Reaction studies identify a cyclometalated iron(
ii
)-methyl species as the key intermediate leading to C-H methylated product upon reaction with oxidant, consistent with a previously proposed iron(
ii
)/iron(
iii
)/iron(
i
) reaction manifold for C-H arylation.
Iron-catalyzed C-H methylation with organoaluminum reagents accesses reactive cyclometalated iron(
ii
) intermediates.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>34782896</pmid><doi>10.1039/d1cc05607g</doi><tpages>4</tpages><orcidid>https://orcid.org/0000-0002-2300-3867</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1359-7345 |
| ispartof | Chemical communications (Cambridge, England), 2021-11, Vol.57 (95), p.12784-12787 |
| issn | 1359-7345 1364-548X |
| language | eng |
| recordid | cdi_rsc_primary_d1cc05607g |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Catalysis Coordination compounds Iron Iron 57 Methylation Oxidizing agents Reagents |
| title | Intermediates and mechanism in iron-catalyzed C-H methylation with trimethylaluminum |
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