Ten-fold boost of catalytic performance in thiol-yne click reaction enabled by a palladium diketonate complex with a hexafluoroacetylacetonate ligand

Palladium complexes with fluorinated acetylacetonate chelating ligands were studied as catalysts for alkyne hydrothiolation. A ten-fold increase in the catalytic efficiency was achieved by using 0.1 mol% of Pd(hfpd)2 complex (hfpd = hexafluoroacetylacetonate) with a variety of thiol-yne coupling partners. The principal possibility of a hundred-fold increase in the efficiency of Pd-catalyzed Markovnikov-type RSH addition with 0.01 mol% of the catalyst was successfully achieved with the hfpd ligand for the first time. The hexafluoroacetylacetonate chelating ligand not only enhanced the affinity of palladium centers to the triple bond of acetylene, but also stabilized the catalytic system against formation of insoluble polymeric [Pd(SPh)2]n species, thus ensuring that the reaction operates homogeneously. Utilizing other diketonate ligands resulted in cocktail-type catalysis with variable and poorly predictable contributions of homogeneous and heterogeneous pathways. © 2018 The Royal Society of Chemistry.

Авторы
Eremin D.B.1 , Boiko D.A.1, 2 , Borkovskaya E.V.1 , Khrustalev V.N. 3 , Chernyshev V.M.4 , Ananikov V.P.1, 2
Редакторы
-
Издательство
Royal Society of Chemistry
Номер выпуска
12
Язык
Английский
Страницы
3073-3080
Статус
Опубликовано
Подразделение
-
Номер
-
Том
8
Год
2018
Организации
  • 1 Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, Moscow, 119991, Russian Federation
  • 2 Chemistry Department, Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow, 119991, Russian Federation
  • 3 Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow, 117198, Russian Federation
  • 4 Platov South-Russian State Polytechnic University (NPI), Prosveschenya 132, Novocherkassk, 346428, Russian Federation
Ключевые слова
Catalysis; Catalysts; Chelation; Efficiency; Ligands; Acetylacetonates; Catalytic efficiencies; Catalytic performance; Catalytic system; Chelating ligands; Diketonate complexes; Palladium complexes; Thiol-yne couplings; Palladium compounds
Дата создания
19.10.2018
Дата изменения
19.10.2018
Постоянная ссылка
https://repository.rudn.ru/ru/records/article/record/7314/