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Ligand-modulated metal–radical polarity match enables general 1,2-dicarbofunctionalization of ethylene

Nature Chemistry (2026) Cite this article

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Abstract

Leveraging transition metal catalysis to direct multiple radical intermediates towards a single desired product offers many synthetic opportunities while presenting an important chemoselectivity challenge arising from selectivity in radical capture by the catalyst. How mechanistic design precisely tunes this selectivity remains limited, constraining the rational design of efficient catalytic systems. Here we demonstrate that the electronic bias of the radical intermediates and the ligand-modulated copper centre can be strategically harnessed to control the selectivity of copper-mediated radical capture. A strongly π-accepting terpyridine ligand modulates the electronic properties of the copper catalyst, enabling the selective capture of radical intermediates with complementary polarity through a metal–radical polarity-match mechanism. Building on this mechanistic framework, we have established a synthetically powerful, yet highly challenging ethylene 1,2-dicarbofunctionalization. This provides streamlined access to structurally diverse, medicinally relevant 1,2-dicarbofunctionalized ethanes that incorporate sp3-, sp2- and sp-hybridized carbogenic functional groups while offering mechanistic insights and design principles that facilitate the rational design of transition metal-catalysed radical transformations.

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Fig. 1: Ligand-modulated selective radical capture through metal–radical polarity match enables generalized photoredox/copper dual-catalysed 1,2-dicarbofunctionalization of ethylene.
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Fig. 2: Ligand effect on the selectivity of 1,2-diarylation of ethylene.
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Fig. 3: Substrate scope of ethylene 1,2-diarylation.
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Fig. 4: Extension of reaction to other carbogenic coupling partners.
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Fig. 5: Extension of reaction to carboxylic acids as C(sp3) synthons.
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Data availability

All of the data supporting the findings of this study are available within the article and its Supplementary Information.

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Acknowledgements

We thank H. T. Ang (NUS) for helpful scientific discussion and substantial contributions to manuscript writing and editing. We thank K. L. Wong (NUS) for help with HRMS experiments. We are grateful for the financial support provided by the SUSTech-NUS Joint Research Program, Ministry of Education (MOE) of Singapore (T2EP10224-0005), the National Research Foundation, the Prime Minister’s Office of Singapore, under its NRF-CRP Programme (NRFCRP25-2020RS-0002), the National Natural Science Foundation of China (22371200) and the NUS (Suzhou) Research Institute, Science and Technology Project of Jiangsu Province (BZ2022056).

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Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, Singapore, Republic of Singapore

    Zhexuan Lei, Chu Wang, Anwei Wang, Tao Liu, Weigang Zhang & Jie Wu

  2. Department of Chemistry, Southern University of Science and Technology, Shenzhen, People’s Republic of China

    Zhe Dong

  3. College of Chemical Engineering, Nanjing Tech University, Nanjing, People’s Republic of China

    Weigang Zhang

  4. National University of Singapore (Suzhou) Research Institute, Suzhou, People’s Republic of China

    Jie Wu

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  1. Zhexuan Lei
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Contributions

Z.L. and J.W. conceived the project. Z.L. developed the system and conducted most of the experimental work. Z.L. and C.W. conducted the computational study. A.W., T.L. and W.Z. assisted with the experiments. Z.D., W.Z. and J.W. supervised and coordinated the project. Z.L., Z.D., W.Z. and J.W. wrote the paper with input from all the authors.

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Correspondence to Zhe Dong, Weigang Zhang or Jie Wu.

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Extended data

Extended Data Fig. 1 Bioactive molecules and natural products encompassing 1,2-dicarbofunctionalized ethane motif.

1,2-Dicarbofunctionalized ethanes are prevalent motifs in medicinal relevant molecules, some selected examples bearing alkyl (sp3), (hetero)aryl (sp2), and alkynyl (sp) carbogenic functional groups are shown. tBu, tert-butyl. OMe, methoxy.

Extended Data Fig. 2 Ethane (C2) bridge represents an important motif in fragment-based drug design (FBDD).

a, Linking two aryl moieties with an ethane bridge allowed the discovery of potent and selective BACE-1 inhibitor with 350-fold potency boost29. b, Dimerized 1,2,4-benzothiadiazine 1,1-dioxide (BTD)-type AMPA potentiator linked by an ethane bridge showed over 104 potency boost30. c, Changing the ether linker in a CREBBP inhibitor to the corresponding ethane linker resulted in over 7-fold potency boost31. d, Linking the ester and phenol functional group with an ethane bridge allowed for an over 4-fold potency boost in the search for BACE-1 inhibitor32. Kd, dissociation constant; EC50, half maximal effective concentration; IC50, half maximal inhibitory concentration; OMe, methoxy.

Extended Data Fig. 3 Application of photoredox/copper dual-catalyzed ethylene 1,2-diarylation to substituted alkenes and 1,3-dienes.

Beyond ethylene, the 1,2-diarylation protocol can be applied to other unsaturated systems, such as subtituted alkene, 1,3-diene, and propylene, another gaseous feedstock chemical. −OTf, trifluoromethanesulfonate; PC, photocatalyst; Ar, aryl; DMB, 4,4′-dimethyl-2,2′-bipyridine; OMe, methoxy; OPh, phenoxy; OTf, trifluoromethanesulfonyloxy; tBu, tert-butyl.

Extended Data Fig. 4 Proposed mechanisms of photoredox/copper dual-catalyzed 1,2-diarylation of ethylene.

The Ru-based photocatalyst operates through a reductive quenching cycle, in which single-electron transfer from the Cu(I) catalyst to the excited-state Ru(II)* species generates ground-state Ru(I). The resulting Ru(I) species reduces the aryl-DBT salt, releasing an aryl radical that undergoes radical addition followed by capture by the copper catalyst. The resulting transient Cu(III) species rapidly undergoes reductive elimination to afford the 1,2-diarylethane product. SET, single electron transfer; −OTf, trifluomethanesulfonate; Ar, aryl; X, ligand; L, ligand; PC, photocatalyst; TfO, trifluoromethanesulfonyloxy.

Extended Data Fig. 5 Proposed mechanisms of photoredox/copper dual-catalyzed 1-aryl-2-alkynylation of ethylene.

The Ru-based photocatalyst operates through a reductive quenching cycle, in which single-electron transfer from the Cu(I) catalyst to the excited-state Ru(II)* species generates ground-state Ru(I). The resulting Ru(I) species reduces the aryl-DBT salt, releasing an aryl radical that undergoes radical addition followed by capture by the copper catalyst. The resulting transient Cu(III) species rapidly undergoes reductive elimination to afford the 1-aryl-2-alkynylethane product. SET, single electron transfer; −OTf, trifluomethanesulfonate; Ar, aryl; X, ligand; L, ligand; R, functional group; PC, photocatalyst; TfO, trifluoromethanesulfonyloxy.

Extended Data Fig. 6 Proposed mechanisms of photoredox/copper dual-catalyzed 1-aryl-2-alkylation of ethylene.

The acridinium-based photocatalyst operates through a reductive quenching cycle, in which single-electron transfer from the carboxylate to the excited-state photocatalyst generates the ground-state reduced photocatalyst. This reduced species then reduces the aryl-DBT salt, releasing an aryl radical that undergoes radical addition followed by capture by the copper catalyst. The alkyl radical generated by decarboxylation subsequently couples with the copper species bearing the primary alkyl group, through either an inner- or outer-sphere pathway, to afford the 1-aryl-2-alkylethane product. SET, single electron transfer; −OTf, trifluomethanesulfonate; Ar, aryl; X, ligand; L, ligand; Alk, alkyl; PC, photocatalyst; TfO, trifluoromethanesulfonyloxy.

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Supplementary Sections 1–7, Figs. 1–36, Tables 1–15, Detailed discussions on mechanistic studies, Characterization data and NMR spectra.

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Lei, Z., Wang, C., Wang, A. et al. Ligand-modulated metal–radical polarity match enables general 1,2-dicarbofunctionalization of ethylene. Nat. Chem. (2026). https://doi.org/10.1038/s41557-026-02177-8

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