24th International Conference on Phosphorus Chemistry (ICPC24)

21 / 2023-07-07 19:58:39

Phosphorylation of terminal acetylenes using diphenylphosphine oxide under electrocatalytic conditions

electrochemical phosphorylation,terminal acetylene,electrochemical reduction

New Technologies in Phosphorus Chemistry > 1) New reagents and methods in organophosphorus Chemistry

Phosphorylation of terminal acetylenes using diphenylphosphine oxide under electrocatalytic conditions

M. Tarasov, V. Khrizanforova, T. Gryasnova, K. Kholin, Y. Budnikova

Institute of Organic and Physical Chemistry. A.E. Arbuzov, Kazan Scientific Center of the Russian Academy of Sciences, Kazan, Russia 420088, Russia, Kazan, st. Academician Arbuzov, 8.

Email : t.maxim1618@gmail.com



Phosphorylation of acetylenes is an important way to obtain practically significant ligands, flame retardants, biologically active compounds, for example, the progesterone receptor antagonist. Depending on the conditions and reagents, the products may contain both a carbon-carbon triple bond, and a double or single bond upon hydrophosphination. The classical routes to phosphorus-substituted alkynes are mostly based on elimination reactions from the corresponding vinylic halide/pseudohalide derivatives or the reaction of a metal acetylide with a halophosphine or a derivative. Despite the success of their synthesis, most reactions are carried out under harsh and hazardous conditions, techniques include elevated temperatures, excess oxidizing agents and expensive radical initiators (such as DBU), catalyst metals, primarily expensive palladium, rhodium and silver, are often based on sulfonyl, halogen and others derivatives. In this regard, the development of an efficient and environmentally benign method for the direct construction of C(sp, sp², sp³)-P bonds through C-H/P-H coupling of acetylenes and phosphine oxides under noble metal- and oxidant-free conditions is still highly desirable.

We demonstrated the ability to direct the phosphorylation of terminal acetylenes along various pathways by varying the conditions of electrosynthesis (solvent, catalyst, background salt, etc.).



The work was carried out with the support of the Russian Science Foundation (project No. 22-13-00017).



Keywords：Electrochemical reduction, electrochemical phosphorylation, terminal acetylene