Expedient Cyano‐hydroxylation of Alkenes Enabled by Halogen Atom Transfer Induced Radical Ring‐Opening Elaboration of 3‐Bromo‐isoxazoline Cycloadducts

Comprehensive Summary Herein, we present a highly efficient one‐pot, two‐step synthesis of β ‐hydroxy nitrile scaffolds, which possess both significant synthetic value and notable biological activity, starting from readily accessible alkenes. This methodology relies crucially on the seamless integration of a highly regioselective (3+2) cycloaddition reaction, employing the commercially available 1,1‐dibromoformaldoxime as the 1,3‐dipole precursor, with a subsequent halogen atom transfer‐induced radical ring‐opening elaboration of the resulting 3‐bromo‐2‐isoxazoline cycloadducts. This protocol is featured by mild reaction conditions, broad alkene scope and various derivatizations of the obtained cyano‐hydroxylation products, offering a versatile and practical pathway to accessing multi‐functionalized molecules.