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

Gnaim, Samer and Bauer, Adriano and Zhang, Hai-Jun and Chen, Longrui and Gannet, Cara and Malapit, Christian A. and Hill, David E. and Vogt, David and Tang, Tianhua and Daley, Ryan A. and Hao, Wei and Zeng, Rui and Quertenmont, Mathilde and Beck, Wesley D. and Kandahari, Elya and Vantourout, Julien C. and Echeverria, Pierre-Georges and Abruna, Hector D. and Blackmond, Donna G. and Minteer, Shelley D. and Reisman, Sarah E. and Sigman, Matthew S. and Baran, Phil S. (2022) Cobalt-electrocatalytic HAT for functionalization of unsaturated C–C bonds. Nature, 605 (7911). pp. 687-695. ISSN 0028-0836. doi:10.1038/s41586-022-04595-3. https://resolver.caltech.edu/CaltechAUTHORS:20211124-184849879

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Abstract

The study and application of transition metal hydrides (TMHs) has been an active area of chemical research since the early 1960s, for energy storage, through the reduction of protons to generate hydrogen , and for organic synthesis, for the functionalization of unsaturated C–C, C–O and C–N bonds. In the former instance, electrochemical means for driving such reactivity has been common place since the 1950s 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). 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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1038/s41586-022-04595-3DOIArticle
https://rdcu.be/cOL5ZPublisherFree ReadCube access
https://doi.org/10.33774/chemrxiv-2021-b34zlDOIDiscussion Paper
ORCID:
AuthorORCID
Bauer, Adriano0000-0002-3376-343X
Malapit, Christian A.0000-0002-8471-4208
Hao, Wei0000-0001-9493-6894
Beck, Wesley D.0000-0001-9202-1017
Kandahari, Elya0000-0002-3163-4888
Vantourout, Julien C.0000-0002-0602-069X
Abruna, Hector D.0000-0002-3948-356X
Blackmond, Donna G.0000-0001-9829-8375
Minteer, Shelley D.0000-0002-5788-2249
Reisman, Sarah E.0000-0001-8244-9300
Sigman, Matthew S.0000-0002-5746-8830
Baran, Phil S.0000-0001-9193-9053
Alternate Title:Cobalt-Electrocatalytic Hydrogen Atom Transfer for Functionalization of Unsaturated C–C Bonds
Additional Information:© 2022 Nature Publishing Group. Received 24 August 2021; Accepted 01 March 2022; Published 25 May 2022; Issue Date 26 May 2022. 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. Data availability: The data that support the findings of this study are available from the corresponding authors upon reasonable request. Contributions: 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. The authors declare no competing interests. Peer review information: Nature thanks the anonymous reviewers for their contribution to the peer review of this work.
Funders:
Funding AgencyGrant Number
NSFCHE-2002158
Council for Higher Education (Israel)UNSPECIFIED
Fulbright FoundationUNSPECIFIED
Yad HanadivUNSPECIFIED
Fonds Wetenschappelijk Onderzoek (FWO)J 4452-N
Shanghai Institute of Organic ChemistryUNSPECIFIED
NIHK99GM140249
Subject Keywords:Electrocatalysis; Synthetic chemistry methodology
Issue or Number:7911
DOI:10.1038/s41586-022-04595-3
Record Number:CaltechAUTHORS:20211124-184849879
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20211124-184849879
Official Citation: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
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112048
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 Nov 2021 19:13
Last Modified:01 Jun 2022 18:11

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