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(sp 3 )–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.