Catalytic construction of P-stereogenic centers through asymmetric hydrophosphination of unsaturated C–C bonds

Abstract

P-Stereogenic centers are important structural motifs prevalent in natural products, bioactive molecules, and high-performance ligands. Their presence confers significant value across medicinal chemistry, materials science, and asymmetric catalysis. In recent years, catalytic asymmetric hydrophosphination has emerged as a powerful and efficient strategy for constructing suchP-stereogenic compounds. Distinguished by high atom economy, broad substrate compatibility, and excellent stereocontrol under mild conditions, these transformations align closely with the principles of sustainable and green synthesis. This review summarizes recent advances in the catalytic asymmetric hydrophosphination of unsaturated C–C bonds for the synthesis ofP-stereogenic centers. It covers substrates including alkenes bearing electron-withdrawing groups, alkynes, as well as specialized systems such as enynes, allenes, and conjugated dienes. Emphasis is placed on the design of catalytic systems, encompassing transition-metal catalysts (e.g., Pd, Ni, Cu, Co, Mn) and organocatalysts, along with their mechanisms. Current challenges, such as the low reactivity of unactivated or sterically hindered substrates and difficulties in achieving stereochemical differentiation between phosphorus substituents, are also discussed. This review aims to provide a reference for further innovation and methodological development in the synthesis of P-stereogenic molecules.

Keywords

P-stereogenic centers / asymmetric hydrophosphination / unsaturated C–C bond / transition-metal catalysis / enantioselective synthesis

Authors contribution

Wang BL, Xing LK, Wang YX: Investigation, writing-original draft, writing-review & editing. Lu Y, Yang XH: Conceptualization, writing-review & editing.

Conflicts of interest

The authors declare no conflicts of interest.

Ethical approval

Not applicable.

Consent to participate

Not applicable.

Consent for publication

Not applicable.

Availability of data and materials

Not applicable.

Funding

The authors are thankful for financial support from the National Natural Science Foundation of China (Nos. 22371016 & 22201018), the Beijing Natural Science Foundation (No. 2262029), and the National Key R&D Program of China (No. 2021YFA1401200).

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