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Nozaki-Hiyama-Kishi (NHK) reactions offer a mild approach for the formation of alcohol motifs through radical-polar crossover-based pathways from various radical precursors. However, the application of multicomponent NHK-type reactions, which allow the formation of multiple bonds in a single step, has been largely restricted to bulky alkyl radical precursors, thus limiting their expanded utilization. Herein, we disclose a general three-component NHK-type reaction enabled by delayed radical-polar crossover, which efficiently tolerates a plethora of radical precursors that were previously unavailable. This method enables the modular assembly of versatile homoallylic alcohols from feedstock chemicals with excellent chemo-, regio-, diastereo-, and enantioselectivities in a single step. Experimental studies and density functional theory (DFT) calculations reveal that the kinetically favored formation of an allylchromium(III) species is paramount for enforcing the delayed radical-polar crossover over direct radical addition. Finally, straightforward transformations and applications of the homoallylic alcohol products were demonstrated, showcasing the synthetic utility of this method.
Li et al. (Wed,) studied this question.