Vinylphosphonates have been known as an important family of organophosphorus compounds with multiple potential applications, which include the synthesis of poly(vinylphosphonate)s for applications such as dental adhesives, in studies of bone regeneration and in the development of proton conducting membranes. Synthesis of these compounds via the addition of P-H bond of (O)P(H)(OR)2 to unsaturated molecules mediated by complexes of rare elements like Rh and Pd is a straightforward strategy to obtain new organophosphorus compounds. However, the use of low earth abundant metals in this kind of transformations remains as a clear disadvantage. Thus, the development of synthetic methodologies involving simpler low–cost commercially available raw materials is highly desired. Herein, we present our findings in the study of the hydrophosphonylation reaction of several alkynes, using readily commercially available trialkylphosphites in the presence of a NiCl2.6H2O catalyst. On the first place, optimization of reaction conditions for the DPA hydrofunctionalisation with P(OiPr)3 is presented. Then, a series of trialkylphosphites and alkynes were tested under the optimized conditions obtaining the corresponding hydrophosphonylation product in yields ranging from good to modest. Control experiments showed the in situ formation of dialkylphosphites, which is presumably the species responsible for the alkyne hydrophosphonylation reaction. Finally, a plausible mechanistic proposal based on the experimental findings of this work and in the literature will be proposed.

Ni(II) catalyzed hydrophosphonylation of alkynes with a P(III) source

254th National Meeting (2017)

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