【Frontiers in HaiChuan Chemical Technology】Peking University team collaborates with the Chinese Academy of Sciences to achieve catalytic reshaping of complex olefins through carbon-carbon double bond degradation
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Catalytic Rearrangement of Complex Olefins via C–C Double Bond Degradation 2025-03-31 14:40:02 Recently, the research team led by Jiao Ning from Peking University, in collaboration with the titanium-silica molecular sieve synthesis and catalytic oxidation team at Sinopec Research Institute of Petrochemical Technology (hereinafter referred to as the Research Institute), published a research paper in Science titled \"Catalytic Rearrangement of Complex Olefins via C–C Double Bond Degradation\". The team discovered an efficient conversion of complex olefins into carbonyl nitriles using heterogeneous copper/multi-porous titanium-silica molecular sieves, which enables the simultaneous introduction of both carbonyl and nitrile functional groups within the molecule, thus allowing for precise modification of the molecular structure of complex organic compounds. It is reported that the cleavage of C=C double bonds holds great significance in chemical synthesis and drug development, but issues such as the high energy of these double bonds, their low reactivity, and the difficulty in controlling product selectivity render this research area highly challenging. Although methods such as olefin metathesis and ozone decomposition have made significant progress in olefin transformation, the approach of reshaping complex molecules by breaking C=C double bonds remains underdeveloped. The research team made progress over 8 years of in-depth research on the key scientific issue of the \"nitration reaction of C=C double bonds\". Based on the intracrystalline pore expansion of titanium-silica molecular sieves and the regulation of titanium states, a research team from the Institute of Stone Sciences successfully prepared composite catalytic materials by highly dispersing CuO nanoclusters in the confined pores of multi-level porous titanium-silica molecular sieves. The CuO nanoclusters are evenly distributed, possessing more exposed active centers, which significantly enhances the catalytic efficiency. Based on these catalytic materials, Jiao Ning’s research team at Peking University achieved efficient and selective oxidation of C=C double bonds into C=O and C≡N bonds by precisely controlling the efficient initiation of azide radicals and the homolysis of O-O bonds, thus realizing an oxygen-based nitration reaction for the efficient breakage of double bonds in alkenes. This reaction is applicable not only to simple olefinic substrates but also to the skeletal remodeling of complex molecules such as steroids, terpenes, and glycosynes, demonstrating broad applicability and high catalytic efficiency. Heterogeneous catalysts feature stable performance and are recyclable, providing a typical example of the integration between organic chemistry and heterogeneous catalysis.
Carbon-carbon bonds constitute the basic framework of organic compounds, and their cleavage and transformation are crucial in areas such as the utilization of fossil fuels, the conversion of waste polyolefins and biomass, and molecular framework modification. For example, oil cracking and pyrolysis in the petrochemical industry, which are carried out under high temperature, high pressure, or catalytic conditions, are essentially processes of breaking carbon-carbon bonds. Carbon-carbon double bonds are widely present in bulk chemicals, natural products, and drug molecules. The reshaping of carbon-carbon double bonds in complex molecules plays an important role in synthetic chemistry and drug discovery (Figure 1A). For a long time, the ways to break and transform carbon-carbon double bonds have been limited, mainly focusing on traditional oxidation reactions and olefin metathesis (which won the 2005 Nobel Prize in Chemistry), which convert carbon-carbon double bonds into carbon-oxygen bonds and new carbon-carbon bonds, respectively. However, the nitridation reaction involving the introduction of a nitrogen atom into the molecule through the cleavage of a carbon-carbon double bond is rarely achieved (Figure 1B). Since nitrogen-containing compounds are widely used in fields such as pesticides, fragrances, dyes, and materials, introducing nitrogen, an important element essential for life, into molecules can significantly enhance their functional properties or suitability as pharmaceuticals. Precise and efficient nitration reactions have therefore always been a focus of synthetic chemistry. However, due to the high bond energy of carbon-carbon bonds, their low reactivity, and the difficulty in controlling selectivity—especially when there are multiple reaction sites in complex molecules and the reaction environment is complex—it is even more challenging to carry out carbon-carbon double bond cleavage and nitration reactions on such molecules (Figure 1C).