Markovnikov hydroamination of terminal alkenes via phosphine redox catalysis

Nature

by Flora Fan

February 23, 2026

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A groundbreaking advancement in organometallic chemistry has been achieved through the development of a phosphine-photoredox catalyst system that enables Markovnikov hydroamination of unactivated terminal alkenes using N–H azoles. This innovation, detailed in a study published in *Nature*, challenges conventional late transition metal catalysis by introducing a novel mechanism involving radical PIV intermediates. Unlike traditional methods, this approach leverages main-group phosphorus elements to mimic transition metal reactivity, achieving reactions that were previously unattainable. The researchers demonstrated that a phosphine radical cation activates the alkene for nucleophilic amination by the azole—a process typically associated with transition metals. This mechanism was supported by experimental and computational studies, revealing how the catalyst system facilitates intermolecular hydroamination with high selectivity for the Markovnikov product. The discovery not only expands substrate tolerance but also opens new possibilities for main-group element catalysis in organic synthesis. The significance of this work lies in its potential to transform chemical synthesis by reducing reliance on transition metals, which are often rare and expensive. By harnessing phosphorus-based catalysts, scientists could develop more sustainable and cost-effective methods for producing valuable compounds, such as pharmaceutical intermediates and advanced materials. This breakthrough underscores the untapped potential of main-group elements in catalysis and highlights the importance of exploring alternative pathways beyond traditional metal-centered

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Originally published on Nature on 2/23/2026