Mechanistic and Preparative Studies of Radical Chain Homolytic Substitution Reactions of N‑Heterocyclic Carbene Boranes and Disulfides
Reactions of 1,3-dimethylimidazol-2-ylidene–borane (diMe-Imd-BH3) and related NHC–boranes with diaryl and diheteroaryl disulfides provide diverse NHC–boryl monosulfides (diMe-Imd-BH2SAr) and NHC–boryl disulfides (diMe-Imd-BH(SAr)2). Heating in the dark with 1 equiv of disulfide favors monosulfide fo...
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| Veröffentlicht in: | Journal of the American Chemical Society 2013-07, Vol.135 (28), p.10484-10491 |
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| creator | Pan, Xiangcheng Vallet, Anne-Laure Schweizer, Stéphane Dahbi, Karim Delpech, Bernard Blanchard, Nicolas Graff, Bernadette Geib, Steven J Curran, Dennis P Lalevée, Jacques Lacôte, Emmanuel |
| description | Reactions of 1,3-dimethylimidazol-2-ylidene–borane (diMe-Imd-BH3) and related NHC–boranes with diaryl and diheteroaryl disulfides provide diverse NHC–boryl monosulfides (diMe-Imd-BH2SAr) and NHC–boryl disulfides (diMe-Imd-BH(SAr)2). Heating in the dark with 1 equiv of disulfide favors monosulfide formation, while irradiation with 2 equiv disulfide favors disulfide formation. With heteroaryl disulfides, the NHC–borane in the primary NHC–boryl sulfide product migrates from sulfur to nitrogen to give new products with a thioamide substructure. Most substitution reactions are thought to proceed through radical chains in which homolytic substitution of a disulfide by an NHC–boryl radical is a key step. However, with electrophilic disulfides under dark conditions, a competing ionic path may also be possible. |
| doi_str_mv | 10.1021/ja403627k |
| format | Article |
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Heating in the dark with 1 equiv of disulfide favors monosulfide formation, while irradiation with 2 equiv disulfide favors disulfide formation. With heteroaryl disulfides, the NHC–borane in the primary NHC–boryl sulfide product migrates from sulfur to nitrogen to give new products with a thioamide substructure. Most substitution reactions are thought to proceed through radical chains in which homolytic substitution of a disulfide by an NHC–boryl radical is a key step. However, with electrophilic disulfides under dark conditions, a competing ionic path may also be possible.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja403627k</identifier><identifier>PMID: 23718209</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Boranes - chemistry ; Chemical Sciences ; Disulfides - chemistry ; Free Radicals - chemical synthesis ; Free Radicals - chemistry ; Heterocyclic Compounds - chemical synthesis ; Heterocyclic Compounds - chemistry ; Methane - analogs & derivatives ; Methane - chemical synthesis ; Methane - chemistry ; Molecular Structure ; Organic chemistry</subject><ispartof>Journal of the American Chemical Society, 2013-07, Vol.135 (28), p.10484-10491</ispartof><rights>Copyright © 2013 American Chemical Society</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a415t-471cbcef5e4eeaab65eb3f683d634255a104ecd788b39a6287f70e0e57a721f93</citedby><cites>FETCH-LOGICAL-a415t-471cbcef5e4eeaab65eb3f683d634255a104ecd788b39a6287f70e0e57a721f93</cites><orcidid>0000-0001-9297-0335 ; 0000-0003-0753-6951</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja403627k$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja403627k$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,777,781,882,2752,27057,27905,27906,56719,56769</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23718209$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-00853043$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Pan, Xiangcheng</creatorcontrib><creatorcontrib>Vallet, Anne-Laure</creatorcontrib><creatorcontrib>Schweizer, Stéphane</creatorcontrib><creatorcontrib>Dahbi, Karim</creatorcontrib><creatorcontrib>Delpech, Bernard</creatorcontrib><creatorcontrib>Blanchard, Nicolas</creatorcontrib><creatorcontrib>Graff, Bernadette</creatorcontrib><creatorcontrib>Geib, Steven J</creatorcontrib><creatorcontrib>Curran, Dennis P</creatorcontrib><creatorcontrib>Lalevée, Jacques</creatorcontrib><creatorcontrib>Lacôte, Emmanuel</creatorcontrib><title>Mechanistic and Preparative Studies of Radical Chain Homolytic Substitution Reactions of N‑Heterocyclic Carbene Boranes and Disulfides</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Reactions of 1,3-dimethylimidazol-2-ylidene–borane (diMe-Imd-BH3) and related NHC–boranes with diaryl and diheteroaryl disulfides provide diverse NHC–boryl monosulfides (diMe-Imd-BH2SAr) and NHC–boryl disulfides (diMe-Imd-BH(SAr)2). Heating in the dark with 1 equiv of disulfide favors monosulfide formation, while irradiation with 2 equiv disulfide favors disulfide formation. With heteroaryl disulfides, the NHC–borane in the primary NHC–boryl sulfide product migrates from sulfur to nitrogen to give new products with a thioamide substructure. Most substitution reactions are thought to proceed through radical chains in which homolytic substitution of a disulfide by an NHC–boryl radical is a key step. However, with electrophilic disulfides under dark conditions, a competing ionic path may also be possible.</description><subject>Boranes - chemistry</subject><subject>Chemical Sciences</subject><subject>Disulfides - chemistry</subject><subject>Free Radicals - chemical synthesis</subject><subject>Free Radicals - chemistry</subject><subject>Heterocyclic Compounds - chemical synthesis</subject><subject>Heterocyclic Compounds - chemistry</subject><subject>Methane - analogs & derivatives</subject><subject>Methane - chemical synthesis</subject><subject>Methane - chemistry</subject><subject>Molecular Structure</subject><subject>Organic chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkctuEzEUhi0EoqGw4AXQbJBgMcV3T5YlXFIpXNTC2jrjOaM4TMapPVMpO5ZseUWepJ6mhA0rX_T937H8E_Kc0TNGOXuzAUmF5ubHAzJjitNSMa4fkhmllJem0uKEPElpk4-SV-wxOeHCsIrT-Yz8-oRuDb1Pg3cF9E3xNeIOIgz-BourYWw8piK0xSU03kFXLNbg-2IZtqHbT5Grsc7RYRx86ItLBDdt7hKf__z8vcQBY3B712V0AbHGHou3IUKfrdO0dz6NXesbTE_Joxa6hM_u11Py_cP7b4tlufry8WJxvipBMjWU0jBXO2wVSkSAWiusRasr0WghuVLAqETXmKqqxRw0r0xrKFJUBgxn7VycktcH7xo6u4t-C3FvA3i7PF_Z6Y7SSgkqxQ3L7KsDu4vhesQ02K1PDrsuvz-MyTJJNTNKM_VP62JIKWJ7dDNqp5LssaTMvrjXjvUWmyP5t5UMvDwA4JLdhDH2-Uf-I7oFp22aaA</recordid><startdate>20130717</startdate><enddate>20130717</enddate><creator>Pan, Xiangcheng</creator><creator>Vallet, Anne-Laure</creator><creator>Schweizer, Stéphane</creator><creator>Dahbi, Karim</creator><creator>Delpech, Bernard</creator><creator>Blanchard, Nicolas</creator><creator>Graff, Bernadette</creator><creator>Geib, Steven J</creator><creator>Curran, Dennis P</creator><creator>Lalevée, Jacques</creator><creator>Lacôte, Emmanuel</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0001-9297-0335</orcidid><orcidid>https://orcid.org/0000-0003-0753-6951</orcidid></search><sort><creationdate>20130717</creationdate><title>Mechanistic and Preparative Studies of Radical Chain Homolytic Substitution Reactions of N‑Heterocyclic Carbene Boranes and Disulfides</title><author>Pan, Xiangcheng ; Vallet, Anne-Laure ; Schweizer, Stéphane ; Dahbi, Karim ; Delpech, Bernard ; Blanchard, Nicolas ; Graff, Bernadette ; Geib, Steven J ; Curran, Dennis P ; Lalevée, Jacques ; Lacôte, Emmanuel</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a415t-471cbcef5e4eeaab65eb3f683d634255a104ecd788b39a6287f70e0e57a721f93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Boranes - chemistry</topic><topic>Chemical Sciences</topic><topic>Disulfides - chemistry</topic><topic>Free Radicals - chemical synthesis</topic><topic>Free Radicals - chemistry</topic><topic>Heterocyclic Compounds - chemical synthesis</topic><topic>Heterocyclic Compounds - chemistry</topic><topic>Methane - analogs & derivatives</topic><topic>Methane - chemical synthesis</topic><topic>Methane - chemistry</topic><topic>Molecular Structure</topic><topic>Organic chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Pan, Xiangcheng</creatorcontrib><creatorcontrib>Vallet, Anne-Laure</creatorcontrib><creatorcontrib>Schweizer, Stéphane</creatorcontrib><creatorcontrib>Dahbi, Karim</creatorcontrib><creatorcontrib>Delpech, Bernard</creatorcontrib><creatorcontrib>Blanchard, Nicolas</creatorcontrib><creatorcontrib>Graff, Bernadette</creatorcontrib><creatorcontrib>Geib, Steven J</creatorcontrib><creatorcontrib>Curran, Dennis P</creatorcontrib><creatorcontrib>Lalevée, Jacques</creatorcontrib><creatorcontrib>Lacôte, Emmanuel</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Pan, Xiangcheng</au><au>Vallet, Anne-Laure</au><au>Schweizer, Stéphane</au><au>Dahbi, Karim</au><au>Delpech, Bernard</au><au>Blanchard, Nicolas</au><au>Graff, Bernadette</au><au>Geib, Steven J</au><au>Curran, Dennis P</au><au>Lalevée, Jacques</au><au>Lacôte, Emmanuel</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanistic and Preparative Studies of Radical Chain Homolytic Substitution Reactions of N‑Heterocyclic Carbene Boranes and Disulfides</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2013-07-17</date><risdate>2013</risdate><volume>135</volume><issue>28</issue><spage>10484</spage><epage>10491</epage><pages>10484-10491</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Reactions of 1,3-dimethylimidazol-2-ylidene–borane (diMe-Imd-BH3) and related NHC–boranes with diaryl and diheteroaryl disulfides provide diverse NHC–boryl monosulfides (diMe-Imd-BH2SAr) and NHC–boryl disulfides (diMe-Imd-BH(SAr)2). Heating in the dark with 1 equiv of disulfide favors monosulfide formation, while irradiation with 2 equiv disulfide favors disulfide formation. With heteroaryl disulfides, the NHC–borane in the primary NHC–boryl sulfide product migrates from sulfur to nitrogen to give new products with a thioamide substructure. Most substitution reactions are thought to proceed through radical chains in which homolytic substitution of a disulfide by an NHC–boryl radical is a key step. However, with electrophilic disulfides under dark conditions, a competing ionic path may also be possible.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>23718209</pmid><doi>10.1021/ja403627k</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0001-9297-0335</orcidid><orcidid>https://orcid.org/0000-0003-0753-6951</orcidid></addata></record> |
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| subjects | Boranes - chemistry Chemical Sciences Disulfides - chemistry Free Radicals - chemical synthesis Free Radicals - chemistry Heterocyclic Compounds - chemical synthesis Heterocyclic Compounds - chemistry Methane - analogs & derivatives Methane - chemical synthesis Methane - chemistry Molecular Structure Organic chemistry |
| title | Mechanistic and Preparative Studies of Radical Chain Homolytic Substitution Reactions of N‑Heterocyclic Carbene Boranes and Disulfides |
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