Cobalt-electrocatalytic HAT for functionalization of unsaturated C–C bonds

Samer Gnaim, Adriano Bauer, Hai-Jun Zhang, Longrui Chen, Cara Gannett, Christian A. Malapit, David E. Hill, David Vogt, Tianhua Tang, Ryan A. Daley, Wei Hao, Rui Zeng, Mathilde Quertenmont, Wesley D. Beck, Elya Kandahari, Julien C. Vantourout, Pierre-Georges Echeverria, Hector D. Abruna (), Donna G. Blackmond (), Shelley D. Minteer (), Sarah E. Reisman (), Matthew S. Sigman () and Phil S. Baran ()
Additional contact information
Samer Gnaim: The Scripps Research Institute (TSRI)
Adriano Bauer: The Scripps Research Institute (TSRI)
Hai-Jun Zhang: The Scripps Research Institute (TSRI)
Longrui Chen: The Scripps Research Institute (TSRI)
Cara Gannett: Cornell University
Christian A. Malapit: University of Utah
David E. Hill: The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology
David Vogt: University of Utah
Tianhua Tang: University of Utah
Ryan A. Daley: The Scripps Research Institute (TSRI)
Wei Hao: The Scripps Research Institute (TSRI)
Rui Zeng: Cornell University
Mathilde Quertenmont: Minakem Recherche
Wesley D. Beck: University of Utah
Elya Kandahari: The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology
Julien C. Vantourout: The Scripps Research Institute (TSRI)
Pierre-Georges Echeverria: Minakem Recherche
Hector D. Abruna: Cornell University
Donna G. Blackmond: The Scripps Research Institute (TSRI)
Shelley D. Minteer: University of Utah
Sarah E. Reisman: The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology
Matthew S. Sigman: University of Utah
Phil S. Baran: The Scripps Research Institute (TSRI)

Nature, 2022, vol. 605, issue 7911, 687-695

Abstract: Abstract The study and application of transition metal hydrides (TMHs) has been an active area of chemical research since the early 1960s1, for energy storage, through the reduction of protons to generate hydrogen2,3, and for organic synthesis, for the functionalization of unsaturated C–C, C–O and C–N bonds4,5. In the former instance, electrochemical means for driving such reactivity has been common place since the 1950s6 but the use of stoichiometric exogenous organic- and metal-based reductants to harness the power of TMHs in synthetic chemistry remains the norm. In particular, cobalt-based TMHs have found widespread use for the derivatization of olefins and alkynes in complex molecule construction, often by a net hydrogen atom transfer (HAT)7. Here we show how an electrocatalytic approach inspired by decades of energy storage research can be made use of in the context of modern organic synthesis. This strategy not only offers benefits in terms of sustainability and efficiency but also enables enhanced chemoselectivity and distinct, tunable reactivity. Ten different reaction manifolds across dozens of substrates are exemplified, along with detailed mechanistic insights into this scalable electrochemical entry into Co–H generation that takes place through a low-valent intermediate.

Date: 2022
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DOI: 10.1038/s41586-022-04595-3

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