Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations
Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This...
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| creator | Marín‐Díaz, Pablo Martínez‐Núñez, Clara Sanz, Roberto Suárez‐Pantiga, Samuel |
| description | Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending on the nucleophile. The reaction is initiated by a halogen‐sulfur bond that causes C−S bond cleavage. Moreover, the reaction with iodine proceeds through homoallyl iodide intermediates.
Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending of the nucleophile. |
| doi_str_mv | 10.1002/ejoc.202400147 |
| format | Article |
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Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending of the nucleophile.</description><identifier>ISSN: 1434-193X</identifier><identifier>EISSN: 1099-0690</identifier><identifier>DOI: 10.1002/ejoc.202400147</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Amines ; carbocations ; Cations ; Cleavage ; Cyclopropane ; C−S bond cleavage ; halogen ; Iodine ; Nucleophiles ; Organosulfur compounds</subject><ispartof>European journal of organic chemistry, 2024-05, Vol.27 (20), p.n/a</ispartof><rights>2024 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH</rights><rights>2024. This article is published under http://creativecommons.org/licenses/by-nc/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c3127-1bf3d121f1fbda1b7aad1c370dc9bb8693ade8adfe2a979ad7ad2164bf444b5a3</cites><orcidid>0000-0002-4433-8295 ; 0009-0001-7667-7769 ; 0000-0003-2830-0892 ; 0000-0002-4249-7807</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fejoc.202400147$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fejoc.202400147$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Marín‐Díaz, Pablo</creatorcontrib><creatorcontrib>Martínez‐Núñez, Clara</creatorcontrib><creatorcontrib>Sanz, Roberto</creatorcontrib><creatorcontrib>Suárez‐Pantiga, Samuel</creatorcontrib><title>Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations</title><title>European journal of organic chemistry</title><description>Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending on the nucleophile. The reaction is initiated by a halogen‐sulfur bond that causes C−S bond cleavage. Moreover, the reaction with iodine proceeds through homoallyl iodide intermediates.
Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending of the nucleophile.</description><subject>Amines</subject><subject>carbocations</subject><subject>Cations</subject><subject>Cleavage</subject><subject>Cyclopropane</subject><subject>C−S bond cleavage</subject><subject>halogen</subject><subject>Iodine</subject><subject>Nucleophiles</subject><subject>Organosulfur compounds</subject><issn>1434-193X</issn><issn>1099-0690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkD1PwzAQhiMEEqWwMltiTvEXST1WoaWgSmUoEpt1ie02VRIXOynKxF_HpQjYmO50ep670xtF1wSPCMb0Vm9tMaKYcowJT0-iAcFCxDgR-DT0nPGYCPZ6Hl14v8UYiyQhg-hjDpVd6wY9O1vbVit0r31Xmc5BW-41yioNe1hrZA3K-qKyO2d3fVXrdtNXaLUpbei08wgahSZ12QTNNgc6jNHMujqs_CMW4PKyCWr2BfrL6MxA5fXVdx1GL7PpKpvHi-XDYzZZxAUjNI1JbpgilBhicgUkTwEUKViKVSHyfJwIBkqPQRlNQaQCVAqKkoTnhnOe3wEbRjfHveGNt077Vm5t55pwUjKchJDGCU0DNTpShbPeO23kzpU1uF4SLA8hy0PI8ifkIIij8F5Wuv-HltOnZfbrfgKSTIUV</recordid><startdate>20240527</startdate><enddate>20240527</enddate><creator>Marín‐Díaz, Pablo</creator><creator>Martínez‐Núñez, Clara</creator><creator>Sanz, Roberto</creator><creator>Suárez‐Pantiga, Samuel</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-4433-8295</orcidid><orcidid>https://orcid.org/0009-0001-7667-7769</orcidid><orcidid>https://orcid.org/0000-0003-2830-0892</orcidid><orcidid>https://orcid.org/0000-0002-4249-7807</orcidid></search><sort><creationdate>20240527</creationdate><title>Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations</title><author>Marín‐Díaz, Pablo ; Martínez‐Núñez, Clara ; Sanz, Roberto ; Suárez‐Pantiga, Samuel</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3127-1bf3d121f1fbda1b7aad1c370dc9bb8693ade8adfe2a979ad7ad2164bf444b5a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Amines</topic><topic>carbocations</topic><topic>Cations</topic><topic>Cleavage</topic><topic>Cyclopropane</topic><topic>C−S bond cleavage</topic><topic>halogen</topic><topic>Iodine</topic><topic>Nucleophiles</topic><topic>Organosulfur compounds</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Marín‐Díaz, Pablo</creatorcontrib><creatorcontrib>Martínez‐Núñez, Clara</creatorcontrib><creatorcontrib>Sanz, Roberto</creatorcontrib><creatorcontrib>Suárez‐Pantiga, Samuel</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>Wiley Online Library Free Content</collection><collection>CrossRef</collection><jtitle>European journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Marín‐Díaz, Pablo</au><au>Martínez‐Núñez, Clara</au><au>Sanz, Roberto</au><au>Suárez‐Pantiga, Samuel</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations</atitle><jtitle>European journal of organic chemistry</jtitle><date>2024-05-27</date><risdate>2024</risdate><volume>27</volume><issue>20</issue><epage>n/a</epage><issn>1434-193X</issn><eissn>1099-0690</eissn><abstract>Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending on the nucleophile. The reaction is initiated by a halogen‐sulfur bond that causes C−S bond cleavage. Moreover, the reaction with iodine proceeds through homoallyl iodide intermediates.
Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending of the nucleophile.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ejoc.202400147</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-4433-8295</orcidid><orcidid>https://orcid.org/0009-0001-7667-7769</orcidid><orcidid>https://orcid.org/0000-0003-2830-0892</orcidid><orcidid>https://orcid.org/0000-0002-4249-7807</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Amines carbocations Cations Cleavage Cyclopropane C−S bond cleavage halogen Iodine Nucleophiles Organosulfur compounds |
| title | Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations |
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