Tuning the Reactivity of Alkoxyl Radicals from Cyclization to 1,2-Silyl Transfer: Stereoselective Synthesis of β-Substituted Cycloalcohols.

Herein, we report a radical strategy for diastereoselective construction of β-substituted cyclopentanols and cyclobutanols. The success of the reaction is attributed to the favorable radical 1,2-silyl transfer over the cyclization of alkoxy radicals to the olefins. The reaction shows broad substrate scope and wide functional-group tolerance. The synthetic potential of the methodology was demonstrated in the gram scale reaction and facile synthesis of various spiro compounds.