Recently, the research group of Professor Weiping Liu, part of the Intelligent Health Management Team led by Professor Tao Yi from the College of Chemistry and Chemical Engineering, has made new progress in the field of manganese-catalyzed asymmetric borrowing hydrogen reactions. This work, titled “Tailored Manganese-Catalyzed Enantioconvergent Hydrophosphination to Access Remote P,C Stereogenic Phosphines”, was published in the internationally renowned journal Journal of the American Chemical Society (JACS).
Chiral phosphine compounds bearing both P- and C-stereocenters are widely used as organocatalysts or transition-metal ligands in organic synthesis. Transition-metal-catalyzed asymmetric hydrophosphination of alkenes offers a direct and atom economic route to chiral phosphines. However, this strategy is typically limited to electron deficient alkenes and mainly generates a single C or P stereocenter. Consequently, the construction of phosphine compounds containing remote P and C stereocenters via asymmetric hydrophosphination remains challenging. Traditional methods often rely on stepwise construction of stereocenters, involving multiple synthetic steps and resulting in low overall efficiency. The borrowing hydrogen strategy, through a dehydrogenation transformation hydrogenation cascade, reduces intermediate isolation steps and avoids the use of external oxidants and reductants, and has become an important platform for achieving atom and step economical synthesis.
Professor Weiping Liu’s research group has been committed to the study of earth abundant metal catalyzed borrowing hydrogen reactions. In previous work, the group developed a series of earth abundant metal catalyzed borrowing hydrogen reactions, achieving atom and step economical redox neutral valorization of simple alcohols (J. Am. Chem. Soc., 2025, 147, 21209 21218; Nat. Commun., 2024, 15, 6798; J. Am. Chem. Soc., 2023, 145, 25545 25552; Angew. Chem. Int. Ed., 2023, 62, e202215882; Angew. Chem. Int. Ed., 2023, 62, e202303433). Recently, by leveraging an asymmetric borrowing hydrogen strategy, the group achieved a manganese catalyzed enantioconvergent hydrophosphination of racemic allylic alcohols. A single catalyst simultaneously controls two remote and flexible P and C stereocenters, enabling the efficient synthesis of chiral γ hydroxy phosphines. Furthermore, the practicality of this catalytic system is demonstrated by its scalability, diverse derivatization reactions, and the successful application of its derivatives as chiral bidentate ligands in asymmetric hydrogenation reactions.
Xin Chen, a Ph.D. candidate (Class of 2022) from the College of Chemistry and Chemical Engineering at our university, and Yue Shi from Tianjin University are the co first authors of the paper. Professor Weiping Liu from our university and Professor Genping Huang from Tianjin University are the co corresponding authors. Donghua University is the first corresponding institution. This research work was supported by the National Natural Science Foundation of China and the “Lizhi Program” Frontier Direction Innovation Team Building Special Fund of our university.
Link to the paper: https://pubs.acs.org/doi/10.1021/jacs.6c02388
