Group 2 Catalysis for the atom-efficient synthesis of imidazolidine and thiazolidine derivatives

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Abstract

A wide variety of functionalised imidazolidine-2-ones and -thiones, 2-imino-imidazolidines and thiazolidine-2-thiones have been synthesised under very mild reaction conditions by using simple and cost-effective alkaline earth bis(amide) precatalysts, [Ae{N(SiMe<inf>3</inf>)<inf>2</inf>}<inf>2</inf>(THF)<inf>2</inf>] (Ae=Mg, Ca, Sr). The reactions ensue with 100 % atom efficiency as one-pot cascades from simple, commercially available terminal alkyne and heterocumulene reagents. The reactions take place through the initial assembly of propargylamidines, which are utilised in subsequent cyclisation reactions through addition of the isocyanate, isothiocyanate and, in one case, carbon disulfide reagents. This reactivity is deduced to take place through a well-defined sequence of heterocumulene hydroacetylenation and alkyne hydroamidation steps, which are all mediated at the alkaline earth centre. The rate and regioselectivity of the cyclisation reactions are, thus, found to be heavily dependent upon the identity of the catalytic alkaline earth centre employed. Similarly, the selectivity of the reactions was observed to be profoundly affected by stereoelectronic variations in the individual substrates, albeit by a similar Group 2-centred reaction mechanism in all cases studied.

Original languageEnglish
Pages (from-to)10548-10557
Number of pages10
JournalChemistry - A European Journal
Volume21
Issue number29
DOIs
Publication statusPublished - 13 Jul 2015

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Imidazolidines
Thiazolidines
Catalysis
Alkynes
Earth (planet)
Cyclization
Derivatives
Atoms
Carbon Disulfide
Thiones
Isocyanates
Regioselectivity
Amides
Substrates
Costs

Keywords

  • alkaline earths metals
  • cascade reactions
  • cycloaddition
  • synthetic methods

Cite this

Group 2 Catalysis for the atom-efficient synthesis of imidazolidine and thiazolidine derivatives. / Arrowsmith, Merle; Hill, Michael S.; Kociok-Kohn, Gabriele.

In: Chemistry - A European Journal, Vol. 21, No. 29, 13.07.2015, p. 10548-10557.

Research output: Contribution to journalArticle

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