Rhodium-Catalyzed Construction of Boron-Based Point and Axially Chirality via Asymmetric Annulation of Alkynylboron Reagents

Rhodium-Catalyzed Construction of Boron-Based Point and Axially Chirality via Asymmetric Annulation of Alkynylboron Reagents | 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 Rhodium-Catalyzed Construction of Boron-Based Point and Axially Chirality via Asymmetric Annulation of Alkynylboron Reagents Xingwei Li, Xiaohan Zhu, Jing Li, Haonan Peng, Mengxia Gong, Wei Zhou, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6359589/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 05 Nov, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Boron-stereogenic and C–B axially chiral compounds featuring boron-based chirality represent a rarely explored class of chiral scaffolds. Reported herein is asymmetric access to boron-stereogenic and C–B axially chiral (hetero)cycles via rhodium-catalyzed C–H activation of (hetero)arenes en route to [4+2] or [3+2] annulation with two classes of boron-functionalized alkynes. The annulation of tetracoordinate gem-dialkynylboron with two classes of arenes afforded B-stereogenic (hetero)cycles via desymmetrization of the diyne. The employment of tricoordinate, sterically hindered boron-functionalized alkynes in [4+2] annulation with a 2-carboxamide-functinalized indole afforded C–B axially chiral biaryls via C(3)–H activation of the indole ring (up to 99% ee). All the coupling reactions proceed with good functional group tolerance, excellent chemoselectivity, and enantioselectivity under mild reaction conditions, requiring no stoichiometric amount of oxidant. The chiral product exhibited limited configurational stability that is intrinsic in boron-based chirality. Moreover, the coupling system allowed delivery of chiral organoboron compounds bearing diverse drug-like molecular scaffolds. Photophysical properties of representative axially chiral products have been explored. Physical sciences/Chemistry/Chemical synthesis/Asymmetric synthesis Physical sciences/Chemistry/Catalysis/Homogeneous catalysis Full Text Additional Declarations There is NO Competing Interest. Supplementary Files 4.cif Rhodium-Catalyzed Construction of Boron-Based Point and Axially Chirality via Asymmetric Annulation of Alkynylboron Reagents 24.cif Rhodium-Catalyzed Construction of Boron-Based Point and Axially Chirality via Asymmetric Annulation of Alkynylboron Reagents 44.cif Rhodium-Catalyzed Construction of Boron-Based Point and Axially Chirality via Asymmetric Annulation of Alkynylboron Reagents SIBZXH0321.pdf Rhodium-Catalyzed Construction of Boron-Based Point and Axially Chirality via Asymmetric Annulation of Alkynylboron Reagents Cite Share Download PDF Status: Published Journal Publication published 05 Nov, 2025 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. 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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-6359589","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":440480637,"identity":"25132972-d07d-4a3b-9e47-3372bd81397f","order_by":0,"name":"Xingwei 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