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Key to the approach is the ability to generate a strong base catalytically, as the desired cyclizations can be problematic under non\u2010catalytic conditions. Substitution reactions catalyzed by Br\u00f8nsted bases often suffer from poor turnover because leaving groups are poorly basic. We put forth a process in which base regeneration does not depend on p\n                    <jats:italic>K<\/jats:italic>\n                    <jats:sub>a<\/jats:sub>\n                    considerations, but on reaction of a fluoride catalyst (Lewis base) with an organosilane (base\u2010embedding electrophile). Our protocol is amenable to an unprecedented broad range of heterocycles and highly functionalized and sterically hindered fluoroarenes. Despite ring strain, direct formation of C\u2500N stereogenic axis can be carried out with linear substrates unbiased for cyclization and with tryptophan\u2010containing peptides. We provide synthesis of drug\u2010like cyclic and atropisomeric molecules which are elusive in medicinal chemistry screenings, as well as a direct macrocyclization route toward stereochemically and structurally diverse atropopeptides, molecules inspired by bioactive and naturally occurring ribosomally synthesized post\u2010translationally modified peptides (RiPPs). This work establishes a unique disconnection toward cyclic heterobiaryl molecules and catalysis that is to unlock other transformations.\n                  <\/jats:p>","DOI":"10.1002\/anie.8290035","type":"journal-article","created":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T07:35:31Z","timestamp":1789976131000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Synthesis of Large\u2010 and Medium\u2010Sized Heterobiaryl Atropisomeric Rings and Atropopeptides by Catalytic Intramolecular S\n                    <sub>N<\/sub>\n                    Ar"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9373-7671","authenticated-orcid":false,"given":"Alireza Abbasi","family":"Kejani","sequence":"first","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences  Prague Czech Republic"},{"name":"Department of Organic Chemistry Faculty of Science Charles University  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-4946-0584","authenticated-orcid":false,"given":"Paritosh","family":"Dey","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences  Prague Czech Republic"},{"name":"Department of Organic Chemistry Faculty of Science Charles University  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8353-7684","authenticated-orcid":false,"given":"Nicholas H.","family":"Stillman","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-4882-3735","authenticated-orcid":false,"given":"Daniel M.","family":"Andrade","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9202-1324","authenticated-orcid":false,"given":"Michal","family":"\u0160imek","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences  Prague Czech Republic"},{"name":"Department of Organic Chemistry Faculty of Science Charles University  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4495-0070","authenticated-orcid":false,"given":"Martin","family":"Dra\u010d\u00ednsk\u00fd","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3100-4293","authenticated-orcid":false,"given":"Daniel","family":"B\u00edm","sequence":"additional","affiliation":[{"name":"Department of Physical Chemistry University of Chemistry and Technology  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0430-8793","authenticated-orcid":false,"given":"Paulo H. 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