【Frontiers in HaiChuan Chemical Technology】Dalian Institute of Chemical Physics proposes a new strategy for nickel-catalyzed cyclic polycondensation of 1,3-butadiene

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The new strategy I proposed for the nickel-catalyzed cyclic telomerization of 1,3-butadiene was published on June 17, 2025. Recently, the research team led by Researcher Chen Qing’an from the Bionic Catalysis Synthesis Research Group (Group 211) in our institute’s Fine Chemicals Research Laboratory made new progress in the functionalization of butadiene through telomerization; they developed a novel nickel (Ni(0)) catalytic system that enabled an unconventional 1,3-functionalization reaction pattern. This strategy generates the LNi(C8H12) intermediate through an oxidative cyclometallation process, which is then subjected to cycloaddition with a dienophile to achieve the efficient construction of chiral bicyclic frameworks, thereby providing a new method for the stereoselective synthesis of complex cyclic molecules. In the field of organic chemistry, developing efficient catalytic systems to achieve diverse transformations of simple starting materials is one of the core goals of synthetic chemistry. Based on the Frontier Orbital Theory (FOT), the reaction selectivity in traditional cyclization reactions involving 1,3-butadiene, such as the Diels-Alder reaction, is primarily governed by the principles of symmetry matching and similar energies; corresponding four-membered or six-membered cyclic products are formed through 1,4- or 1,2-addition. Furthermore, under transition metal-catalyzed conditions, 1,3-butadiene can also undergo oligomerization, either on its own or with other dibindene compounds, to yield octagonal or decagonal cyclic products. However, achieving the synthesis of cyclic products with an odd number of atoms (2n+1) requires unconventional 1,3-functionalization reactions of butadiene, making selective control more challenging. In this work, the team built on their long-term research on the functionalization of 1,3-diene groups (Angew. Chem. Int. Ed., 2019 ； Angew. Chem. Int. Ed., 2020 ； Angew. Chem. Int. Ed., 2021 ； Angew. Chem. Int. Ed., 2022 ； Nat. Catal., 2022 ； Angew. Chem. Int. Ed., 2023 ； Nat. Commun., 2023 ； Nat. Commun., 2023), building on previous nickel-catalyzed cyclometallation reactions (Angew. Chem. Int. Ed., 2023 ； Cell Rep. Phys. Sci., 2023) developed an unconventional nickel-catalyzed stereoselective 1,3-cyclocondensation strategy for 1,3-butadiene and dibienes to construct bicyclic chiral frameworks with excellent enantioselectivity. Mechanistic studies and DFT calculations revealed that the reaction proceeds via the oxidative cyclometallation of Ni(0) with butadiene, and the ringed skeleton is formed through cycloaddition followed by reductive elimination. The reaction products can undergo various derivative modifications, showing good potential for synthetic applications. This work provides new pathways for the diversified transformation of 1,3-butadiene, and also offers insights for the development of asymmetric ring polycondensation reactions. The relevant research findings were published in the Journal of the American Chemical Society under the title “Stereoselective 1,3-Cyclotelomerization of Butadiene with Dienophiles under Nickel Catalysis”. The first author of this work is Li Ying, a doctoral graduate from Group 211 of my institute. The aforementioned research work was funded by projects such as the **National Natural Science Foundation.