Synthesis 2024; 56(03): 399-407
DOI: 10.1055/a-2218-9298

Boron Lewis Acid Catalyzed Hydrophosphorylation of N-Heteroaryl-Substituted Alkenes

Soojin Kwak
Jeongin Choi
This work was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2021R1A2C4001752).


The hydrophosphorylation of N-heteroaryl-substituted alkenes catalyzed by a boron Lewis acid catalyst is reported. This reaction occurs with a range of alkenes bearing N-heterocycles, including pyridines, a quinoline, a pyrrole, and a benzothiazole, resulting in the production of β-N-heteroaryl alkylphosphonates in good yields under additive-free, operationally simple conditions. The mechanistic insights suggest that this hydrophosphorylation involves the deprotonation of the P–H bond of dialkyl phosphites, enabled by the cooperative effects of a boron acid and the basic N-heterocyclic moiety of the alkenes. The resulting phosphonate anion serves as an effective phosphorus nucleophile for the conjugate addition to the concurrently formed N-protonated alkenes. These β-N-heteroaryl alkylphosphonates can be further converted into other valuable organophosphorus compounds through the introduction of an alcohol group or the reduction of the phosphine oxide moiety.

Supporting Information

Publication History

Received: 23 October 2023

Accepted after revision: 28 November 2023

Accepted Manuscript online:
28 November 2023

Article published online:
02 January 2024

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