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

Abstract

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.

Key words

main-group chemistry - organophosphorus compounds - carbon–phosphorus bond - cooperative deprotonation

Publikationsverlauf

Eingereicht: 23. Oktober 2023

Angenommen nach Revision: 28. November 2023

Accepted Manuscript online:
28. November 2023

Artikel online veröffentlicht:
02. Januar 2024

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