CHEMICAL SCIENCE

A new strategy for catalytic reconstruction of all-carbon ring framework


Recently, the research team of Chen Qingan of the Biomimetic Catalytic Synthesis Research Group (Group 211) of the Dalian Institute of Chemistry, Chinese Academy of Sciences, has made new progress in the skeleton rearrangement reaction of seven-membered and eight-membered carbon ring compounds. The team used metal regulation strategies to solve the problem of chemical selectivity in cycloheptantriene hydrogenation reaction and achieve the precise synthesis of 1,2-dihydroquinoline compounds. The team also developed a reaction mode of acid-catalyzed carbon ring skeleton reconstruction using cyclone-based raw materials under the study and inspiration of the reaction mechanism.

The development of efficient preparation methods for complex organic compounds is the unremitting pursuit of synthetic chemists, which plays an important role in promoting the development of natural product total synthesis, drug development, materials science and chemical industry. Using the cyclic molecular backbone of existing compounds, molecular editing and post-modification reactions can provide a faster and more convenient path for the preparation of related compounds.

Chen Qingan’s team has been committed to the development of different catalytic systems to achieve the precise conversion of olefins and alkynes. On the basis of previous relevant research (Angew. Chem. Int. Ed.,2019;Angew. Chem. Int. Ed.,2020;Angew. Chem. Int. Ed.,2021;Angew. Chem. Int. Ed.,2021;Angew. Chem. Int. Ed.,2021;Nat. Commun.,2021;Angew. Chem. Int. Ed.,2022;Nat. Chem., 2022; Nat. Catal., 2022), in this work, the team used a rhodium/acid synergistic catalytic system to achieve selective hydrogenamination of cycloheptantrienes to generate 1,2-dihydroquinoline compounds with a parallel ring structure. The mechanism study showed that the reaction underwent continuous hydrogenamination, inverse-Mannich ring opening and Povarov cyclization to achieve the process of all-carbon ring skeleton reconstruction. Under the guidance of the reaction mechanism, the team found that if cyclic enones are used as the reaction raw material, the synthesis of such products can also be achieved under the catalysis of simple hydrochloric acid. This study provides new ideas for the skeleton editing and rearrangement reactions of circular molecules.

The study, titled “Skeleton-Reorganizing Coupling Reactions of Cycloheptatriene and Cycloalkenones with Amines”, was published in Angew. Chem. Int. Ed.) The first author of this work is Ji Dingwei, a postdoctoral fellow in our institute. The above work was supported by the National Natural Science Foundation of China and other projects. (Source: Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

Related paper information:https://doi.org/10.1002/anie.202213074

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