Synthesis of γ-Iodo-allylic Diboronic Esters via Atom Transfer Radical Addition of (Diborylmethyl)iodide to Alkynes

Herein, we disclose a manganese-catalyzed approach that enables the direct iododiborylcarbofunctionalization of alkynes with a (diboronmethyl)iodide under mild conditions. This approach grants access to a range of structurally unique and synthetically useful γ-iodine-substituted <i>gem</i>-bis(boronate)s, which have hitherto been inaccessible. This atom-economical strategy displays excellent functional-group tolerance, encompasses a wide range of applicable substrates, and demonstrates a high <i>Z</i>:<i>E</i> selectivity (up to 96:4).