Protic Ionic Liquid as Reagent, Catalyst, and Solvent: 1-Methylimidazolium Thiocyanate

We propose a new concept of the triple role of protic ionic liquids with nucleophilic anions: a) a regenerable solvent, b) a Brønsted acid inducing diverse transformations via general acid catalysis, and c) a source of a nucleophile. The efficiency of this strategy was demonstrated using thiocyanate-based protic ionic liquids for the ring-opening of donor-acceptor cyclopropanes. A wide variety of activated cyclopropanes were found to react with 1-methylimidazolium thiocyanate under mild metal-free conditions via unusual nitrogen attack of the ambident thiocyanate ion on the electrophilic center of the three-membered ring affording pyrrolidine-2-thiones bearing donor and acceptor substituents at the C(5) and C(3) atoms, respectively, in a single time-efficient step. The ability of 1-methylimidazolium thiocyanate to serve as a triplex reagent was exemplarily illustrated by (4+2)-annulation with 1-acyl-2-(2-hydroxyphenyl)cyclopropane, epoxide ring-opening and other organic transformations. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Andreev I.A.1, 2 , Ratmanova N.K.1 , Augustin A.U.3 , Ivanova O.A. 2, 4 , Levina I.I.5 , Khrustalev V.N. 2, 6 , Werz D.B.3 , Trushkov I.V. 1, 2
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  • 1 Dmitry Rogachev National Medical Research Center of Pediatric Hematology, Oncology and Immunology, Samory Mashela 1, Moscow, 117997, Russian Federation
  • 2 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow, 119991, Russian Federation
  • 3 Technische Universität Braunschweig, Institute of Organic Chemistry, Hagenring 30, Braunschweig, 38106, Germany
  • 4 Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1–3, Moscow, 119991, Russian Federation
  • 5 Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow, 119334, Russian Federation
  • 6 Faculty of Science, RUDN University, Miklukho-Maklaya 6, Moscow, 117198, Russian Federation
Ключевые слова
(iso)thiocyanates; donor-acceptor cyclopropanes; ionic liquids; nitrogen heterocycles; small ring systems
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