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We report a conformational control strategy that enables remote meta-selective C\u2013H borylation of mono- and 1,2-disubstituted (poly)arenes via arene \u03c0-complexation with Cr(CO)3. The chromium tripod adopts a preferred conformation, exposing the meta-C\u2013H bond, while a tailored iridium catalyst bearing 2-aminophenanthroline ligands reinforces this effect and overrides intrinsic substrate bias. In polyaromatics, the chromium tripod acts as both a conformational director and an electronic modulator, enabling site- and ring-selectivity, which is inaccessible with existing nondirected methods. Computational studies at a state-of-the-art DFT theoretical level support a cooperative origin of selectivity arising from the interplay between arene \u03c0-complexation and the catalyst.<\/jats:p>","DOI":"10.1021\/jacs.6c05911","type":"journal-article","created":{"date-parts":[[2026,7,20]],"date-time":"2026-07-20T06:40:51Z","timestamp":1784529651000},"page":"33191-33205","source":"Crossref","is-referenced-by-count":0,"title":["Conformation-Guided\nRemote C\u2013H Functionalization\nof Aromatic Compounds"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1238-6209","authenticated-orcid":true,"given":"Anup","family":"Mandal","sequence":"first","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8715-2597","authenticated-orcid":true,"given":"Clemens","family":"Maurer","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mohammad","family":"Zafar","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amrita","family":"Chaudhuri","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xujiang","family":"Zhu","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5429-6340","authenticated-orcid":true,"given":"Kavin Raj Kumar","family":"Chandramohan","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3196-6273","authenticated-orcid":true,"given":"Tim K.","family":"Schramm","sequence":"additional","affiliation":[{"name":"University of Bonn , , Beringstra\u00dfe 4 , ,","place":["Bonn, Germany, 53115"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3911-2478","authenticated-orcid":true,"given":"Christoph","family":"Plett","sequence":"additional","affiliation":[{"name":"University of Bonn , , Beringstra\u00dfe 4 , ,","place":["Bonn, Germany, 53115"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6987-4126","authenticated-orcid":true,"given":"Marianne","family":"Engeser","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gregor","family":"Schnakenburg","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5844-4371","authenticated-orcid":true,"given":"Stefan","family":"Grimme","sequence":"additional","affiliation":[{"name":"University of Bonn , , Beringstra\u00dfe 4 , ,","place":["Bonn, Germany, 53115"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3880-8182","authenticated-orcid":true,"given":"Ala","family":"Bunescu","sequence":"additional","affiliation":[{"name":"University of Bonn , , Gerhard-Domagk-Stra\u00dfe 1 , ,","place":["Bonn, Germany, 53121"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,20]]},"reference":[{"issue":"22","key":"2026081210100298300_cit1","doi-asserted-by":"publisher","first-page":"13389","DOI":"10.1021\/acs.jmedchem.0c00915","article-title":"Analysis of Benzenoid\nSubstitution Patterns in Small Molecule Active Pharmaceutical Ingredients","volume":"63","author":"Nilova","year":"2020","journal-title":"J. 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