Hydrogen Bonding Template Enables Remote Meta-C–H Alkenylation of Nitroarenes

Hydrogen Bonding Template Enables Remote Meta-C–H Alkenylation of Nitroarenes | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Hydrogen Bonding Template Enables Remote Meta-C–H Alkenylation of Nitroarenes Debabrata Maiti, Bishal Dutta, Mayank Mahajan, Animesh Ghosh, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3906318/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 30 Aug, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Regioselective distal C-H functionalization of nitroarenes by overriding proximal C-H activation has remained an unsolved challenge. Herein, we present a palladium-catalyzed meta -C-H alkenylation of nitroarene substrate, achieved through leveraging the non-covalent hydrogen bonding interactions. Urea-based templates comprising an elongated biphenyl linker designed in such a way that it interacts with nitro group via strong hydrogen bonding interaction, while a cyano based directing group is attached along the template to coordinate with the palladium centre, thereby facilitating the activation of the remote meta -C-H bond of nitrobenzene. Computational mechanistic investigation and the analysis of non-covalent interaction deciphers the crucial role of H-bonding in regulating the regioselectivity. Physical sciences/Chemistry/Catalysis/Homogeneous catalysis Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology Full Text Additional Declarations Yes there is potential Competing Interest. Patent application no. 202321079920 has been filed. Supplementary Files checkcif.pdf DATASET 1 SupplementaryMaterial.pdf Hydrogen Bonding Template Enables Remote Meta-C–H Alkenylation of Nitroarenes Cite Share Download PDF Status: Published Journal Publication published 30 Aug, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3906318","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":271034538,"identity":"09157423-b622-4247-99a7-575839bcf3c9","order_by":0,"name":"Debabrata Maiti","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA4klEQVRIie3OIQ+CQBTA8Ze0KFQp8hUeM1icn+WYGxZkbBSjyaIfBmfRdhvBgtqc2wW9YtKNqBvBO5RgAJzJcP8djGP32zsAleofo3JhD1BuCALJ/pIqQtHJCX5HxBO9CACWHs7SDhGPEn9vduszAmc/9aAenYGvionBHBQXY9Z6vg3lxQJoOAh2XEyQkYwQPI4yYk/ABbCnZWSYCLIjeLq9iX6tIq6cQsWU5pu0KqYYzPVpjAMrjEehgJ2g1rogLSMaGy6Tcdo3cbNd8Hva9nR9wPmjhHxE5auWf6hUKpXq957zB1uBbKE42gAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0001-8353-1306","institution":"Indian Institute of Technology Bombay","correspondingAuthor":true,"prefix":"","firstName":"Debabrata","middleName":"","lastName":"Maiti","suffix":""},{"id":271034539,"identity":"2544acfe-3115-45d3-8e2e-4342b869392d","order_by":1,"name":"Bishal Dutta","email":"","orcid":"","institution":"Indian Institute of Technology Bombay","correspondingAuthor":false,"prefix":"","firstName":"Bishal","middleName":"","lastName":"Dutta","suffix":""},{"id":271034540,"identity":"58c71909-2fcb-45fd-9837-9888f51a9337","order_by":2,"name":"Mayank Mahajan","email":"","orcid":"","institution":"Indian Institute of Technology Mandi","correspondingAuthor":false,"prefix":"","firstName":"Mayank","middleName":"","lastName":"Mahajan","suffix":""},{"id":271034541,"identity":"1be28bcc-623f-4dda-a404-bbb5d5eca28b","order_by":3,"name":"Animesh Ghosh","email":"","orcid":"","institution":"Indian Institute of Technology Bombay","correspondingAuthor":false,"prefix":"","firstName":"Animesh","middleName":"","lastName":"Ghosh","suffix":""},{"id":271034542,"identity":"f661cbae-ccb0-49d2-8d32-41a5d74adee3","order_by":4,"name":"Maciej Dajek","email":"","orcid":"https://orcid.org/0000-0002-7955-6743","institution":"wroclaw university of science and technology","correspondingAuthor":false,"prefix":"","firstName":"Maciej","middleName":"","lastName":"Dajek","suffix":""},{"id":271034543,"identity":"fc89051e-6790-43c5-adbb-f74cff366003","order_by":5,"name":"Rafal Kowalczyk","email":"","orcid":"","institution":"wroclaw university of science and technology","correspondingAuthor":false,"prefix":"","firstName":"Rafal","middleName":"","lastName":"Kowalczyk","suffix":""},{"id":271034544,"identity":"2295771f-38e6-4fe1-ab7f-561773a3d4f5","order_by":6,"name":"Bhaskar Mondal","email":"","orcid":"","institution":"School of Basic Sciences, Indian Institute of Technology Mandi","correspondingAuthor":false,"prefix":"","firstName":"Bhaskar","middleName":"","lastName":"Mondal","suffix":""},{"id":271034545,"identity":"1c574b6b-bd9f-4607-b25b-bc3c2034a23c","order_by":7,"name":"Haibo Ge","email":"","orcid":"https://orcid.org/0000-0001-6727-4602","institution":"Texas Tech University","correspondingAuthor":false,"prefix":"","firstName":"Haibo","middleName":"","lastName":"Ge","suffix":""}],"badges":[],"createdAt":"2024-01-28 16:25:37","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3906318/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3906318/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-024-51764-1","type":"published","date":"2024-08-30T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":63682249,"identity":"50254076-837c-4de0-8b5c-2e13a51ac0f2","added_by":"auto","created_at":"2024-08-31 07:07:27","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1772416,"visible":true,"origin":"","legend":"","description":"","filename":"Manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3906318/v1_covered_2226fc54-1951-4314-a166-ac4201352429.pdf"},{"id":50704239,"identity":"6368c6ad-6463-4ab8-a057-57e5b682a1f8","added_by":"auto","created_at":"2024-02-06 05:25:27","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":300983,"visible":true,"origin":"","legend":"DATASET 1","description":"","filename":"checkcif.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3906318/v1/fdd71d428ae921554606993b.pdf"},{"id":50704240,"identity":"10a412a3-cc42-4cc5-a01d-fad4458d6352","added_by":"auto","created_at":"2024-02-06 05:25:29","extension":"pdf","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":8119588,"visible":true,"origin":"","legend":"\u003cp\u003eHydrogen Bonding Template Enables Remote Meta-C–H Alkenylation of Nitroarenes\u003c/p\u003e","description":"","filename":"SupplementaryMaterial.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3906318/v1/5d21347e0ff316703876eded.pdf"}],"financialInterests":"\u003cb\u003eYes\u003c/b\u003e there is potential Competing Interest.\nPatent application no. 202321079920 has been filed.","formattedTitle":"Hydrogen Bonding Template Enables Remote Meta-C–H Alkenylation of Nitroarenes","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-3906318/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3906318/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eRegioselective distal C-H functionalization of nitroarenes by overriding proximal C-H activation has remained an unsolved challenge. Herein, we present a palladium-catalyzed \u003cem\u003emeta\u003c/em\u003e-C-H alkenylation of nitroarene substrate, achieved through leveraging the non-covalent hydrogen bonding interactions. Urea-based templates comprising an elongated biphenyl linker designed in such a way that it interacts with nitro group via strong hydrogen bonding interaction, while a cyano based directing group is attached along the template to coordinate with the palladium centre, thereby facilitating the activation of the remote \u003cem\u003emeta\u003c/em\u003e-C-H bond of nitrobenzene. Computational mechanistic investigation and the analysis of non-covalent interaction deciphers the crucial role of H-bonding in regulating the regioselectivity.\u003c/p\u003e","manuscriptTitle":"Hydrogen Bonding Template Enables Remote Meta-C–H Alkenylation of Nitroarenes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-02-06 05:25:22","doi":"10.21203/rs.3.rs-3906318/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"caa6d56f-d85b-4301-930b-79d7c45cc9db","owner":[],"postedDate":"February 6th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":28561620,"name":"Physical sciences/Chemistry/Catalysis/Homogeneous catalysis"},{"id":28561621,"name":"Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology"}],"tags":[],"updatedAt":"2024-08-31T07:07:20+00:00","versionOfRecord":{"articleIdentity":"rs-3906318","link":"https://doi.org/10.1038/s41467-024-51764-1","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2024-08-30 04:00:00","publishedOnDateReadable":"August 30th, 2024"},"versionCreatedAt":"2024-02-06 05:25:22","video":"","vorDoi":"10.1038/s41467-024-51764-1","vorDoiUrl":"https://doi.org/10.1038/s41467-024-51764-1","workflowStages":[]},"version":"v1","identity":"rs-3906318","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3906318","identity":"rs-3906318","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}