Alkoxide-Free Zirconium-Catalyzed Borylation of Unactivated Alkyl Chlorides and Poly(vinyl chloride)

The direct borylation of bench-stable and readily available alkyl chlorides offers an attractive method to produce versatile alkyl boronates and functional group-grafted polyvinyl chloride (PVC). However, current borylation techniques rely on precious metal catalysts or stoichiometric strong bases, which limit their application in PVC modification. In this study, we report a photoinduced zirconocene-catalyzed borylation of various chloroalkanes, utilizing earth-abundant zirconium catalysis and triethylamine as a mild additive under blue light. Mechanistic investigations indicate a radical pathway involving ligand-to-metal charge-transfer (LMCT)-generated Zr(III) species for selective C(sp3)–Cl bond cleavage. Importantly, this method achieves chemoselective PVC borylation without dehydrochlorination or significant chain scission, enabling the upcycling of PVC waste into adhesive materials without requiring plasticizer removal.