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Cobalt-Electrocatalytic Hydrogen Atom Transfer 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 and Vogt, David and Tang, Tianhua and Daley, Ryan and Hao, Wei and Quertenmont, Mathilde and Beck, Wesley D. and Kandahari, Elya and Vantourout, Julien C. and Echeverria, Pierre-Georges and Abruna, Hector and Blackmond, Donna and Minteer, Shelley and Reisman, Sarah and Sigman, Matthew S. and Baran, Phil S. (2021) Cobalt-Electrocatalytic Hydrogen Atom Transfer for Functionalization of Unsaturated C–C Bonds. . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20211124-184849879

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Abstract

The study and application of transition metal hydrides (TMH) has been an active area of chemical research since the early 1960’s. The use of TMHs has been broadly bifurcated into fields focused on energy storage through the reduction of protons to generate hydrogen and in 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 commonplace since the 1950’s. In contrast, the use of stoichiometric exogenous organic and metal-based reductants to harness the power of TMHs in synthetic chemistry remains the norm. In particular, Co-based TMHs have found widespread use for the derivatization of olefins and alkynes in complex molecule construction, often via a net hydrogen atom transfer (HAT). Here, we show how an electrocatalytic approach inspired by decades of energy storage precedent can be leveraged in the context of modern organic synthesis. Such an approach not only offers benefits in terms of sustainability and efficiency but also enables enhanced chemoselectivity and unique and tunable reactivity. Ten different reaction manifolds across dozens of substrates are thus exemplified, along with a detailed mechanistic and computational analysis of this scalable electrochemical entry into Co-H chemistry.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
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
Kandahari, Elya0000-0002-3163-4888
Vantourout, Julien C.0000-0002-0602-069X
Abruna, Hector0000-0002-3948-356X
Blackmond, Donna0000-0001-9829-8375
Minteer, Shelley0000-0002-5788-2249
Reisman, Sarah0000-0001-8244-9300
Sigman, Matthew S.0000-0002-5746-8830
Baran, Phil S.0000-0001-9193-9053
Additional Information:The content is available under CC BY 4.0 License CreativeCommons.org. This work was supported by the NSF Center for Synthetic Organic Electrochemistry, CHE-2002158. S.G. thanks the Council for Higher Education, Fulbright Israel and Yad Hanadiv for the generous fellowships. A.B. thanks the Austrian Science Fund (FWF) for an Erwin Schrödinger Fellowship (J 4452-N). H.-J.Z. thanks the SIOC fellowship. C. A. M. thanks the National Institute of General Medical Sciences of the National Institutes of Health (K99GM140249). The authors 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 HPLC, high-resolution mass spectroscopy and LCMS. We also thank Dr Y. Kawamata, Dr. K.X. Rodriguez and C. Bi for helpful advice and suggestions. Data availability: The data that support the findings of this study are available from the corresponding authors upon reasonable request. The author(s) have declared they have no conflict of interest with regard to this content. The author(s) have declared ethics committee/IRB approval is not relevant to this content.
Funders:
Funding AgencyGrant Number
NSFCHE-2002158
Council for Higher Education (Israel)UNSPECIFIED
Fulbright FoundationUNSPECIFIED
Yad HanadivUNSPECIFIED
Fonds Wetenschappelijk Onderzoek (FWO)J 4452-N
American Institute of Chemical Engineers (AIChE)UNSPECIFIED
NIHK99GM140249
Subject Keywords:electrochemistry; HAT catalysis; organic synthesis; synthetic methodology; electrocatalysis
DOI:10.33774/chemrxiv-2021-b34zl
Record Number:CaltechAUTHORS:20211124-184849879
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20211124-184849879
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:24 Nov 2021 19:13

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