Loading…
Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes
Electrochemical oxidative C–H/N–H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C–H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room tempe...
Saved in:
Published in: | Journal of the American Chemical Society 2018-06, Vol.140 (25), p.7913-7921 |
---|---|
Main Authors: | , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
cited_by | cdi_FETCH-LOGICAL-a361t-4f900cf4ce1fd1dd550f95bcf9e9c1fb6d4258cb36e4ff3ffd50dc21a98e5fe93 |
---|---|
cites | cdi_FETCH-LOGICAL-a361t-4f900cf4ce1fd1dd550f95bcf9e9c1fb6d4258cb36e4ff3ffd50dc21a98e5fe93 |
container_end_page | 7921 |
container_issue | 25 |
container_start_page | 7913 |
container_title | Journal of the American Chemical Society |
container_volume | 140 |
creator | Mei, Ruhuai Sauermann, Nicolas Oliveira, João C. A Ackermann, Lutz |
description | Electrochemical oxidative C–H/N–H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C–H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C–H activation catalysis, generating H2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C–H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C–H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C–H/N–H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature. |
doi_str_mv | 10.1021/jacs.8b03521 |
format | article |
fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_2047262300</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2047262300</sourcerecordid><originalsourceid>FETCH-LOGICAL-a361t-4f900cf4ce1fd1dd550f95bcf9e9c1fb6d4258cb36e4ff3ffd50dc21a98e5fe93</originalsourceid><addsrcrecordid>eNptULFOwzAUtBAISmFjRh4ZSGs7cZqMVVRopYouZY4c-1mkuDHYaSGd-Af-kC8hUQssLO_pne7u6Q6hK0oGlDA6XAnpB0lBQs7oEepRzkjAKYuPUY8QwoJREodn6Nz7VXtGLKGn6IylCWUpG_VQMzEga2cdrO1WFAbw0gkJBrzH00Y5sSsVeKytw5kthKmDTNTCNDtQ-CANFu-lEnW5BZx9fXxOhw_dxGPZQi1sK_xW1k94VtXgKmHw2Dw3FfgLdKKF8XB52H30eDdZZtNgvrifZeN5IMKY1kGkU0KkjiRQrahSnBOd8kLqFFJJdRGriPFEFmEMkdah1ooTJRkVaQJcQxr20c3e98XZ1w34Ol-Xvk1oRAV243NGohGLWUhIS73dU6Wz3jvQ-Ysr18I1OSV5V3belZ0fym7p1wfnTbEG9Uv-affvdada2U0X3__v9Q3Ip4yO</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2047262300</pqid></control><display><type>article</type><title>Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)</source><creator>Mei, Ruhuai ; Sauermann, Nicolas ; Oliveira, João C. A ; Ackermann, Lutz</creator><creatorcontrib>Mei, Ruhuai ; Sauermann, Nicolas ; Oliveira, João C. A ; Ackermann, Lutz</creatorcontrib><description>Electrochemical oxidative C–H/N–H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C–H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C–H activation catalysis, generating H2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C–H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C–H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C–H/N–H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.8b03521</identifier><identifier>PMID: 29812927</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2018-06, Vol.140 (25), p.7913-7921</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a361t-4f900cf4ce1fd1dd550f95bcf9e9c1fb6d4258cb36e4ff3ffd50dc21a98e5fe93</citedby><cites>FETCH-LOGICAL-a361t-4f900cf4ce1fd1dd550f95bcf9e9c1fb6d4258cb36e4ff3ffd50dc21a98e5fe93</cites><orcidid>0000-0001-7034-8772</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29812927$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mei, Ruhuai</creatorcontrib><creatorcontrib>Sauermann, Nicolas</creatorcontrib><creatorcontrib>Oliveira, João C. A</creatorcontrib><creatorcontrib>Ackermann, Lutz</creatorcontrib><title>Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Electrochemical oxidative C–H/N–H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C–H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C–H activation catalysis, generating H2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C–H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C–H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C–H/N–H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNptULFOwzAUtBAISmFjRh4ZSGs7cZqMVVRopYouZY4c-1mkuDHYaSGd-Af-kC8hUQssLO_pne7u6Q6hK0oGlDA6XAnpB0lBQs7oEepRzkjAKYuPUY8QwoJREodn6Nz7VXtGLKGn6IylCWUpG_VQMzEga2cdrO1WFAbw0gkJBrzH00Y5sSsVeKytw5kthKmDTNTCNDtQ-CANFu-lEnW5BZx9fXxOhw_dxGPZQi1sK_xW1k94VtXgKmHw2Dw3FfgLdKKF8XB52H30eDdZZtNgvrifZeN5IMKY1kGkU0KkjiRQrahSnBOd8kLqFFJJdRGriPFEFmEMkdah1ooTJRkVaQJcQxr20c3e98XZ1w34Ol-Xvk1oRAV243NGohGLWUhIS73dU6Wz3jvQ-Ysr18I1OSV5V3belZ0fym7p1wfnTbEG9Uv-affvdada2U0X3__v9Q3Ip4yO</recordid><startdate>20180627</startdate><enddate>20180627</enddate><creator>Mei, Ruhuai</creator><creator>Sauermann, Nicolas</creator><creator>Oliveira, João C. A</creator><creator>Ackermann, Lutz</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-7034-8772</orcidid></search><sort><creationdate>20180627</creationdate><title>Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes</title><author>Mei, Ruhuai ; Sauermann, Nicolas ; Oliveira, João C. A ; Ackermann, Lutz</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a361t-4f900cf4ce1fd1dd550f95bcf9e9c1fb6d4258cb36e4ff3ffd50dc21a98e5fe93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mei, Ruhuai</creatorcontrib><creatorcontrib>Sauermann, Nicolas</creatorcontrib><creatorcontrib>Oliveira, João C. A</creatorcontrib><creatorcontrib>Ackermann, Lutz</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mei, Ruhuai</au><au>Sauermann, Nicolas</au><au>Oliveira, João C. A</au><au>Ackermann, Lutz</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2018-06-27</date><risdate>2018</risdate><volume>140</volume><issue>25</issue><spage>7913</spage><epage>7921</epage><pages>7913-7921</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><notes>ObjectType-Article-1</notes><notes>SourceType-Scholarly Journals-1</notes><notes>ObjectType-Feature-2</notes><notes>content type line 23</notes><abstract>Electrochemical oxidative C–H/N–H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C–H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C–H activation catalysis, generating H2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C–H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C–H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C–H/N–H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>29812927</pmid><doi>10.1021/jacs.8b03521</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0001-7034-8772</orcidid></addata></record> |
fulltext | fulltext |
identifier | ISSN: 0002-7863 |
ispartof | Journal of the American Chemical Society, 2018-06, Vol.140 (25), p.7913-7921 |
issn | 0002-7863 1520-5126 |
language | eng |
recordid | cdi_proquest_miscellaneous_2047262300 |
source | American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list) |
title | Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes |
url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-09-21T22%3A44%3A06IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Electroremovable%20Traceless%20Hydrazides%20for%20Cobalt-Catalyzed%20Electro-Oxidative%20C%E2%80%93H/N%E2%80%93H%20Activation%20with%20Internal%20Alkynes&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Mei,%20Ruhuai&rft.date=2018-06-27&rft.volume=140&rft.issue=25&rft.spage=7913&rft.epage=7921&rft.pages=7913-7921&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/jacs.8b03521&rft_dat=%3Cproquest_cross%3E2047262300%3C/proquest_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a361t-4f900cf4ce1fd1dd550f95bcf9e9c1fb6d4258cb36e4ff3ffd50dc21a98e5fe93%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=2047262300&rft_id=info:pmid/29812927&rfr_iscdi=true |