A Bidentate Iodine(III)‐Based Halogen‐Bond Donor as a Powerful Organocatalyst
In contrast to iodine(I)‐based halogen bond donors, iodine(III)‐derived ones have only been used as Lewis acidic organocatalysts in a handful of examples, and in all cases they acted in a monodentate fashion. Herein, we report the first application of a bidentate bis(iodolium) salt as organocatalyst...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2021-03, Vol.60 (10), p.5069-5073 |
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| creator | Heinen, Flemming Reinhard, Dominik L. Engelage, Elric Huber, Stefan M. |
| description | In contrast to iodine(I)‐based halogen bond donors, iodine(III)‐derived ones have only been used as Lewis acidic organocatalysts in a handful of examples, and in all cases they acted in a monodentate fashion. Herein, we report the first application of a bidentate bis(iodolium) salt as organocatalyst in a Michael and a nitro‐Michael addition reaction as well as in a Diels–Alder reaction that had not been activated by noncovalent organocatalysts before. In all cases, the performance of this bidentate XB donor distinctly surpassed the one of arguably the currently strongest iodine(I)‐based organocatalyst. Bidentate coordination to the substrate was corroborated by a structural analysis and by DFT calculations of the transition states. Overall, the catalytic activity of the bis(iodolium) system approaches that of strong Lewis acids like BF3.
The first application of a bidentate iodine(III)‐based halogen bond donor as organocatalyst is presented. In three benchmark reactions, it markedly outperforms “classical” iodine(I)‐based noncovalent organocatalysts. The bidentate mode of activation as well as the crucial relevance of halogen bonding are confirmed by comparison experiments. |
| doi_str_mv | 10.1002/anie.202013172 |
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The first application of a bidentate iodine(III)‐based halogen bond donor as organocatalyst is presented. In three benchmark reactions, it markedly outperforms “classical” iodine(I)‐based noncovalent organocatalysts. The bidentate mode of activation as well as the crucial relevance of halogen bonding are confirmed by comparison experiments.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>ISSN: 1521-3773</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202013172</identifier><identifier>PMID: 33215804</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Catalytic activity ; Communication ; Communications ; Diels–Alder cycloaddition ; halogen bonding ; hypervalent iodine ; Iodine ; Michael reaction ; noncovalent interactions ; organocatalysis ; Structural analysis ; Substrates</subject><ispartof>Angewandte Chemie International Edition, 2021-03, Vol.60 (10), p.5069-5073</ispartof><rights>2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH</rights><rights>2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><rights>2020. This article is published under http://creativecommons.org/licenses/by/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><citedby>FETCH-LOGICAL-c5712-d77b346cb0685e2da01b4d083ba0e60d7172529be44ac132ab7cd7b74e231f623</citedby><cites>FETCH-LOGICAL-c5712-d77b346cb0685e2da01b4d083ba0e60d7172529be44ac132ab7cd7b74e231f623</cites><orcidid>0000-0002-4125-159X</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%2Fanie.202013172$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202013172$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,780,784,885,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33215804$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Heinen, Flemming</creatorcontrib><creatorcontrib>Reinhard, Dominik L.</creatorcontrib><creatorcontrib>Engelage, Elric</creatorcontrib><creatorcontrib>Huber, Stefan M.</creatorcontrib><title>A Bidentate Iodine(III)‐Based Halogen‐Bond Donor as a Powerful Organocatalyst</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>In contrast to iodine(I)‐based halogen bond donors, iodine(III)‐derived ones have only been used as Lewis acidic organocatalysts in a handful of examples, and in all cases they acted in a monodentate fashion. Herein, we report the first application of a bidentate bis(iodolium) salt as organocatalyst in a Michael and a nitro‐Michael addition reaction as well as in a Diels–Alder reaction that had not been activated by noncovalent organocatalysts before. In all cases, the performance of this bidentate XB donor distinctly surpassed the one of arguably the currently strongest iodine(I)‐based organocatalyst. Bidentate coordination to the substrate was corroborated by a structural analysis and by DFT calculations of the transition states. Overall, the catalytic activity of the bis(iodolium) system approaches that of strong Lewis acids like BF3.
The first application of a bidentate iodine(III)‐based halogen bond donor as organocatalyst is presented. In three benchmark reactions, it markedly outperforms “classical” iodine(I)‐based noncovalent organocatalysts. The bidentate mode of activation as well as the crucial relevance of halogen bonding are confirmed by comparison experiments.</description><subject>Catalytic activity</subject><subject>Communication</subject><subject>Communications</subject><subject>Diels–Alder cycloaddition</subject><subject>halogen bonding</subject><subject>hypervalent iodine</subject><subject>Iodine</subject><subject>Michael reaction</subject><subject>noncovalent interactions</subject><subject>organocatalysis</subject><subject>Structural analysis</subject><subject>Substrates</subject><issn>1433-7851</issn><issn>1521-3773</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkbtu2zAUhomiQe5rx0JAF3eQw5tEeSlgp7kICJIWSGbiSDx2ZcikS0oNvOUR8ox5ktBw4qZdMpEEP37gf35CPjE6ZJTyE7ANDjnllAmm-AeyzzLOUqGU-Bj3UohUFRnbIwchzCNfFDTfJXtCcJYVVO6Tn-Nk0hi0HXSYlM40FgdlWX59enicQECTXELrZmjXZ2dN8t1Z5xMICSQ_3D36ad8mN34G1tXQQbsK3RHZmUIb8PhlPSR352e3p5fp1c1FeTq-SutMMZ4apSoh87qieZEhN0BZJQ0tRAUUc2pUjJPxUYVSQs0Eh0rVRlVKIhdsmnNxSL5tvMu-WqCpYwYPrV76ZgF-pR00-t8b2_zSM_dHq1GRS1FEweBF4N3vHkOnF02osW3BouuD5jIXccaZWqNf_kPnrvc2xovUiMUJC8kiNdxQtXcheJxuP8OoXrel123pbVvxwee3Ebb4az0RGG2A-6bF1Ts6Pb4uz_7KnwHRYKHQ</recordid><startdate>20210301</startdate><enddate>20210301</enddate><creator>Heinen, Flemming</creator><creator>Reinhard, Dominik L.</creator><creator>Engelage, Elric</creator><creator>Huber, Stefan M.</creator><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>24P</scope><scope>WIN</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-4125-159X</orcidid></search><sort><creationdate>20210301</creationdate><title>A Bidentate Iodine(III)‐Based Halogen‐Bond Donor as a Powerful Organocatalyst</title><author>Heinen, Flemming ; Reinhard, Dominik L. ; Engelage, Elric ; Huber, Stefan M.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5712-d77b346cb0685e2da01b4d083ba0e60d7172529be44ac132ab7cd7b74e231f623</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Catalytic activity</topic><topic>Communication</topic><topic>Communications</topic><topic>Diels–Alder cycloaddition</topic><topic>halogen bonding</topic><topic>hypervalent iodine</topic><topic>Iodine</topic><topic>Michael reaction</topic><topic>noncovalent interactions</topic><topic>organocatalysis</topic><topic>Structural analysis</topic><topic>Substrates</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Heinen, Flemming</creatorcontrib><creatorcontrib>Reinhard, Dominik L.</creatorcontrib><creatorcontrib>Engelage, Elric</creatorcontrib><creatorcontrib>Huber, Stefan M.</creatorcontrib><collection>Wiley Online Library (Open Access Collection)</collection><collection>Wiley Online Library Free Content</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Heinen, Flemming</au><au>Reinhard, Dominik L.</au><au>Engelage, Elric</au><au>Huber, Stefan M.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Bidentate Iodine(III)‐Based Halogen‐Bond Donor as a Powerful Organocatalyst</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2021-03-01</date><risdate>2021</risdate><volume>60</volume><issue>10</issue><spage>5069</spage><epage>5073</epage><pages>5069-5073</pages><issn>1433-7851</issn><issn>1521-3773</issn><eissn>1521-3773</eissn><abstract>In contrast to iodine(I)‐based halogen bond donors, iodine(III)‐derived ones have only been used as Lewis acidic organocatalysts in a handful of examples, and in all cases they acted in a monodentate fashion. 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The first application of a bidentate iodine(III)‐based halogen bond donor as organocatalyst is presented. In three benchmark reactions, it markedly outperforms “classical” iodine(I)‐based noncovalent organocatalysts. The bidentate mode of activation as well as the crucial relevance of halogen bonding are confirmed by comparison experiments.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>33215804</pmid><doi>10.1002/anie.202013172</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-4125-159X</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Catalytic activity Communication Communications Diels–Alder cycloaddition halogen bonding hypervalent iodine Iodine Michael reaction noncovalent interactions organocatalysis Structural analysis Substrates |
| title | A Bidentate Iodine(III)‐Based Halogen‐Bond Donor as a Powerful Organocatalyst |
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