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.
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Data availability
The data that support the findings of this study are available from the corresponding authors upon reasonable request.
References
Norton, J. R. & Sowa, J. Introduction: metal hydrides. Chem. Rev. 116, 8315–8317 (2016).
Luo, G. G. et al. Recent progress in ligand-centered homogeneous electrocatalysts for hydrogen evolution reaction. Inorg. Chem. Front. 6, 343–354 (2019).
Margarit, C. G., Asimow, N. G., Thorarinsdottir, A. E., Costentin, C. & Nocera, D. G. Impactful role of cocatalysts on molecular electrocatalytic hydrogen production. ACS Catal. 11, 4561–4567 (2021).
Shevick, S. L. et al. Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals. Chem. Sci. 11, 12401–12422 (2020).
Armstrong, K. C. & Waymouth, R. M. Electroreduction of benzaldehyde with a metal–ligand bifunctional hydroxycyclopentadienyl molybdenum (II) hydride. Organometallics 39, 4415–4419 (2020).
Vesborg, P. C., Seger, B. & Chorkendorff, I. B. Recent development in hydrogen evolution reaction catalysts and their practical implementation. J. Phys. Chem. 6, 951–957 (2015).
Crossley, S. W., Obradors, C., Martinez, R. M. & Shenvi, R. A. Mn-, Fe-, and Co-catalyzed radical hydrofunctionalizations of olefins. Chem. Rev. 116, 8912–9000 (2016).
Wiedner, E. S. et al. Thermodynamic hydricity of transition metal hydrides. Chem. Rev. 116, 8655–8692 (2016).
Hu, Y., Shaw, A. P., Estes, D. P. & Norton, J. R. Transition-metal hydride radical cations. Chem. Rev. 116, 8427–8462 (2016).
Eisenberg, D. C. & Norton, J. R. Hydrogen‐atom transfer reactions of transition‐metal hydrides. Isr. J. Chem 31, 55–66 (1991).
Puls, F., Linke, P., Kataeva, O. & Knölker, H. J. Iron‐catalyzed wacker‐type oxidation of olefins at room temperature with 1, 3‐diketones or neocuproine as ligands. Angew. Chem, Int. Ed. 60, 14083–14090 (2021).
Isayama, S. & Mukaiyama, T. A new method for preparation of alcohols from olefins with molecular oxygen and phenylsilane by the use of bis (acetylacetonato) cobalt (II). Chem. Lett. 18, 1071–1074 (1989).
Gui, J. et al. Practical olefin hydroamination with nitroarenes. Science 348, 886–891 (2015).
Lo, J. C., Gui, J., Yabe, Y., Pan, C. M. & Baran, P. S. Functionalized olefin cross-coupling to construct carbon–carbon bonds. Nature 516, 343–348 (2014).
Gaspar, B. & Carreira, E. M. Mild cobalt‐catalyzed hydrocyanation of olefins with tosyl cyanide. Angew. Chem. In. Ed. 46, 4519–4522 (2007).
Shigehisa, H., Aoki, T., Yamaguchi, S., Shimizu, N. & Hiroya, K. Hydroalkoxylation of unactivated olefins with carbon radicals and carbocation species as key intermediates. J. Am. Chem. Soc. 135, 10306–10309 (2013).
Leggans, E. K., Barker, T. J., Duncan, K. K. & Boger, D. L. Iron (III)/NaBH4-mediated additions to unactivated alkenes: synthesis of novel 20′-vinblastine analogues. Org. Lett. 14, 1428–1431 (2012).
Song, L. et al. Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes. Nat. Chem. 12, 747–754 (2020).
Wells, A. S. On the perils of unexpected silane generation. Org. Process Res. Dev. 14, 484–484 (2010).
Yu, K., Yao, F., Zeng, Q., Xie, H. & Ding, H. Asymmetric total syntheses of (+)-davisinol and (+)-18-benzoyldavisinol: A HAT-initiated transannular redox radical approach. J Am. Chem. Soc. 143, 10576–10581 (2021).
Godfrey, N. A., Schatz, D. J. & Pronin, S. V. Twelve-step asymmetric synthesis of (−)-nodulisporic acid C. J. Am. Chem. Soc. 140, 12770–12774 (2018).
Kellett, R. M. & Spiro, T. G. Cobalt (I) porphyrin catalysts of hydrogen production from water. Inorg. Chem. 24, 2373–2377 (1985).
Zhang, W., Cui, L. & Liu, J. Recent advances in cobalt-based electrocatalysts for hydrogen and oxygen evolution reactions. J. Alloy. Compd 821, 153542 (2020).
Wiedner, E. S. & Bullock, R. M. Electrochemical detection of transient cobalt hydride intermediates of electrocatalytic hydrogen production. J. Am. Chem. Soc. 138, 8309–8318 (2016).
Marinescu, S. C., Winkler, J. R. & Gray, H. B. Molecular mechanisms of cobalt-catalyzed hydrogen evolution. Proc. Natl Acad. Sci. USA 109, 15127–15131 (2012).
Beyene, B. B., Mane, S. B. & Hung, C. H. Electrochemical hydrogen evolution by cobalt (II) porphyrins: effects of ligand modification on catalytic activity, efficiency and overpotential. J. Electrochem. Soc. 165, 481 (2018).
Queyriaux, N., Jane, R. T., Massin, J., Artero, V. & Chavarot-Kerlidou, M. Recent developments in hydrogen evolving molecular cobalt (II)–polypyridyl catalysts. Coordin. Chem. Rev. 304, 3–19 (2015).
Kapat, A., Sperger, T., Guven, S. & Schoenebeck, F. E-Olefins through intramolecular radical relocation. Science 363, 391–396 (2019).
Crossley, S. W., Barabé, F. & Shenvi, R. A. Simple, chemoselective, catalytic olefin isomerization. J. Am. Chem. Soc. 136, 16788–16791 (2014).
Li, G. et al. Radical isomerization and cycloisomerization initiated by H• transfer. J. Am. Chem. Soc. 138, 7698–7704 (2016).
Kingston, C. et al. A survival guide for the “electro-curious”. Acc. Chem. Res. 53, 72–83 (2019).
Gao, Y. et al. Electrochemical Nozaki–Hiyama–Kishi coupling: scope, applications, and mechanism. J. Am. Chem. Soc. 143, 9478–9488 (2021).
Gnaim, S. et al. Electrochemically driven desaturation of carbonyl compounds. Nat. Chem. 13, 367–372 (2021).
Lo, J. C. et al. Fe-catalyzed C–C bond construction from olefins via radicals. J. Am. Chem. Soc. 139, 2484–2503 (2017).
Felpin, F. X. & Fouquet, E. A useful, reliable and safer protocol for hydrogenation and the hydrogenolysis of O‐benzyl groups: the in situ preparation of an active Pd0/C catalyst with well‐defined properties. Chem. Eur. J. 16, 12440–12445 (2010).
Friedfeld, M. R., Margulieux, G. W., Schaefer, B. A. & Chirik, P. J. Bis (phosphine) cobalt dialkyl complexes for directed catalytic alkene hydrogenation. J. Am. Chem. Soc. 136, 13178–13181 (2014).
Liu, X. et al. Cobalt-catalyzed regioselective olefin isomerization under kinetic control. J. Am. Chem. Soc. 140, 6873–6882 (2018).
Kamei, Y. et al. Silane-and peroxide-free hydrogen atom transfer hydrogenation using ascorbic acid and cobalt-photoredox dual catalysis. Nat. Commun. 12, 966 (2021).
Van der Puyl, V., McCourt, R. O. & Shenvi, R. A. Cobalt-catalyzed alkene hydrogenation by reductive turnover. Tetrahedron Lett. 72, 153047 (2021).
Raya, B., Biswas, S. & RajanBabu, T. V. Selective cobalt-catalyzed reduction of terminal alkenes and alkynes using (EtO)2Si(Me)H as a stoichiometric reductant. ACS Catal. 6, 6318–6323 (2016).
Yin, Y. N., Ding, R. Q., Ouyang, D. C., Zhang, Q. & Zhu, R. Highly chemoselective synthesis of hindered amides via cobalt-catalyzed intermolecular oxidative hydroamidation. Nat. Commun. 12, 2552 (2021).
Benkeser, R. A., Schroll, G. & Sauve, D. M. Reduction of organic compounds by lithium in low molecular weight amines. II. Stereochemistry. Chemical reduction of an isolated non-terminal double bond. J. Am. Chem. Soc. 77, 3378–3379 (1955).
Fürstner, A. trans-hydrogenation, gem-hydrogenation, and trans-hydrometalation of alkynes: an interim report on an unorthodox reactivity paradigm. J. Am. Chem. Soc. 141, 11–24 (2018).
Walaijai, K., Cavill, S. A., Whitwood, A. C., Douthwaite, R. E. & Perutz, R. N. Electrocatalytic proton reduction by a cobalt (III) hydride complex with phosphinopyridine PN ligands. Inorg. Chem. 59, 18055–18067 (2020).
Hickey, D. P. et al. Investigating the role of ligand electronics on stabilizing electrocatalytically relevant low-valent Co (I) intermediates. J. Am. Chem. Soc. 141, 1382–1392 (2019).
Qi, X. J., Li, Z., Fu, Y., Guo, Q. X. & Liu, L. Anti-spin-delocalization effect in Co−C bond dissociation enthalpies. Organometallics 27, 2688–2698 (2008).
Yang, Y. et al. Operando methods in electrocatalysis. ACS Catal. 11, 1136–1178 (2021).
Acknowledgements
This work was supported by the NSF Center for Synthetic Organic Electrochemistry (grant no. CHE-2002158). S.G. thanks the Council for Higher Education, Fulbright Israel and Yad Hanadiv for their generous fellowships. A.B. thanks the Austrian Science Fund (FWF) for an Erwin Schrödinger Fellowship (J 4452-N). H.-J.Z. thanks the Shanghai Institute of Organic Chemistry (SIOC) fellowship. C.A.M. thanks the National Institute of General Medical Sciences of the National Institutes of Health (grant no. K99GM140249). We are grateful to D.-H. Huang and L. Pasternack (Scripps Research) for assistance with the NMR spectroscopy, to J. Chen, B. Sanchez and E. Sturgell (Scripps Automated Synthesis Facility) for assistance with high-performance liquid chromatography, high-resolution mass spectroscopy and liquid chromatography–mass spectrometry. We thank S. Harwood, Y. Kawamata, K. X. Rodriguez and C. Bi for helpful advice and suggestions. We also thank Q. Liu and X. Liu (Tsinghua University) for helpful discussions.
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S.G., A.B. and P.S.B. developed the concept. S.G., A.B., H.-J.Z. and P.S.B. were responsible for the optimization and scope. L.C., M.Q., S.G. and P.-G.E. performed the flow setup and scale up. C.G., C.A.M., W.D.B., S.G., H.D.A. and S.D.M. carried out the CV studies and analysis. D.V., T.T. and M.S.S. carried out the DFT calculations and analysis. D.E.H., E.K. and S.E.R. carried out the UV–vis studies. R.A.D., W.H. and D.G.B. carried out the kinetic studies. R.Z. and H.D.A. performed the DEMS analysis. S.G., A.B., H.-J.Z., J.C.V., D.G.B., H.D.A., S.E.R., M.S.S. and P.S.B. prepared the manuscript.
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Gnaim, S., Bauer, A., Zhang, HJ. et al. Cobalt-electrocatalytic HAT for functionalization of unsaturated C–C bonds. Nature 605, 687–695 (2022). https://doi.org/10.1038/s41586-022-04595-3
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DOI: https://doi.org/10.1038/s41586-022-04595-3
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