Scientists from the Zelinsky Institute have discovered a new example of an interrupted Nef reaction

Interrupted reaction is a process in which a known chemical transformation is redirected in a different route by changing the conditions for its occurrence or the structure of the starting compounds. For a long time, such reactions were considered as side processes that chemists tried to suppress in order to achieve the best efficiency of the target transformation. In recent years, interest in interrupted reactions has increased significantly, because this approach allows one to selectively obtain a wide range of different products from the same initial substrates.

Researchers from the Laboratory of Organic and Metal-Organic Nitrogen-Oxygen Systems of the ZIOC discovered the first example of an interrupted Nef reaction in the series of nitrone ethers. The classic Nef reaction is the acidic hydrolysis of nitro compounds to the corresponding carbonyl derivatives. Scientists have shown for the first time that the treatment of cyclic nitrone ethers with hydrogen chloride leads to ring opening and the formation of geminal chloronitroso compounds. This process is the Nef reaction selectively interrupted by an external nucleophile (in this case, chloride ion). It is interesting that the stereochemistry of the discovered transformation depends on the temperature, and in some cases it is possible to carry out a stereodivergent synthesis of products. The developed synthetic approach opens easy access to little-known, but promising for use in fine organic synthesis, hydroxy-substituted chloronitroso compounds.

Source:

Roman S. Malykhin, Yaroslav D. Boyko, Yulia V. Nelyubina, Sema L. Ioffe, and Alexey Yu. Sukhorukov Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted a-Chloronitroso Compounds // J. Org. Chem. 2022, 87, 16617–16631. DOI: 10.1021/acs.joc.2c02281.