biostudies-literatureUnknown28(51)Deng HChina Scholarship CouncilChina Sponsorship CouncilMax-Planck-GesellschaftThe fine-tuning of metal-phosphine-catalyzed reactions relies largely on accessing ever more precisely tuned phosphine ligands by de-novo synthesis. Late-stage C-H functionalization and diversification of commercial phosphines offers rapid access to entire libraries of derivatives based on privileged scaffolds. But existing routes, relying on phosphorus-directed transformations, only yield functionalization of C sp2 -H bonds in a specific position relative to phosphorus. In contrast to phosphorus-directed strategies, herein we disclose an orthogonal functionalization strategy capable of introducing a range of substituents into previously inaccessible positions on arylphosphines. The strongly coordinating phosphine group acts solely as a bystander in the sterically controlled borylation of Chemistry (Weinheim an der Bergstrasse, Germany)e202202074https://www.ebi.ac.uk/biostudies/studies/S-EPMC9544633biostudies-literatureSterically Controlled Late-Stage Functionalization of Bulky Phosphines.PMC9544633Bengsch MTchorz NDeng HNeumann CNfalseSterically Controlled Late-Stage Functionalization of Bulky Phosphines.The fine-tuning of metal-phosphine-catalyzed reactions relies largely on accessing ever more precisely tuned phosphine ligands by de-novo synthesis. Late-stage C-H functionalization and diversification of commercial phosphines offers rapid access to entire libraries of derivatives based on privileged scaffolds. But existing routes, relying on phosphorus-directed transformations, only yield functionalization of C sp2 -H bonds in a specific position relative to phosphorus. In contrast to phosphorus-directed strategies, herein we disclose an orthogonal functionalization strategy capable of introducing a range of substituents into previously inaccessible positions on arylphosphines. The strongly coordinating phosphine group acts solely as a bystander in the sterically controlled borylation of 2022-01-01T00:00:00Z2022 Sep2025-04-04T20:04:09.208Z2025-04-04T20:04:09.208ZS-EPMC95446333578904810.1002/chem.202202074