The review highlights the author’s recent discovery of the radical (co)polymerization ability of alkenylboronic acid derivatives and C–B bond-cleaving side-chain replacement in polymer reaction. The polymerization ability is attributed to the vacant p-orbital of boron, which can stabilize chain-growth radical species. In copolymerization and controlled polymerization, the boron monomer behaves as a relatively electron-rich and conjugated monomer. The boron attached to the polymer main chain was replaceable with other elements, providing access to various polymers of which synthesis is not straightforward, such as poly(α-methyl vinyl alcohol), poly(vinyl alcohol-co-styrene), and poly(ethylene-co-acrylate).
