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Herein, we report a titanium-catalyzed Suzuki\u2013Miyaura cross-coupling of aryl halides with arylboronic acid derivatives. This protocol provides efficient access to a wide range of biaryl (hetero) frameworks in up to 98% yield across 60 examples with promising functional group tolerance. Its practical utility is highlighted by a gram-scale reaction and late-stage modifications, including the synthesis of an Orelabrutinib core intermediate. Preliminary mechanistic experiments, including radical-trapping, isotope-labeling, electrochemical, Hammett, and crossover studies, reveal reactivity features distinct from those commonly observed in conventional Suzuki\u2013Miyaura cross-coupling. These observations provide experimental constraints for future mechanistic investigations of this titanium-catalyzed transformation.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c02686","type":"journal-article","created":{"date-parts":[[2026,8,15]],"date-time":"2026-08-15T15:02:07Z","timestamp":1786806127000},"page":"10697-10702","source":"Crossref","is-referenced-by-count":0,"title":["Titanium-catalyzed\nCross-coupling of Aryl Boronate\nDerivatives and Aryl Halides en Route to Biaryl Backbones"],"prefix":"10.1021","volume":"28","author":[{"given":"Biao","family":"Ma","sequence":"first","affiliation":[{"name":"Northeast Forestry University , , ,","place":["Harbin, China, 150040"]},{"name":"Northeast Forestry University , , ,","place":["Harbin, P. R. China, 150040"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yingning","family":"Mao","sequence":"additional","affiliation":[{"name":"Northeast Forestry University , , ,","place":["Harbin, China, 150040"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guohao","family":"Zhou","sequence":"additional","affiliation":[{"name":"Northeast Forestry University , , ,","place":["Harbin, China, 150040"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaoping","family":"Xue","sequence":"additional","affiliation":[{"name":"Henan Agricultural University , , , ,","place":["Zhengzhou, Henan, China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7822-4560","authenticated-orcid":true,"given":"Jinsong","family":"Peng","sequence":"additional","affiliation":[{"name":"Northeast Forestry University , , ,","place":["Harbin, China, 150040"]},{"name":"Northeast Forestry University , , ,","place":["Harbin, P. R. China, 150040"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-8396-1857","authenticated-orcid":true,"given":"Zhanyu","family":"Li","sequence":"additional","affiliation":[{"name":"Northeast Forestry University , , ,","place":["Harbin, China, 150040"]},{"name":"Northeast Forestry University , , ,","place":["Harbin, P. R. China, 150040"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chunxia","family":"Chen","sequence":"additional","affiliation":[{"name":"Northeast Forestry University , , ,","place":["Harbin, China, 150040"]},{"name":"Northeast Forestry University , , ,","place":["Harbin, P. R. 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