Geometry-Retentive C-Alkenylation of Lithiated α-Aminonitriles: Quaternary α-Alkenyl Amino Acids and Hydantoins

Josep Mas-Roselló, Shuji Hachisu, Jonathan Clayden*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

4 Citations (Scopus)
252 Downloads (Pure)

Abstract

α-Amino nitriles tethered to alkenes through a urea linkage undergo intramolecular C-alkenylation on treatment with base by attack of the lithionitrile derivatives on the N′-alkenyl group. A geometry-retentive alkene shift affords stereospecifically the E or Z isomer of the 5-alkenyl-4-iminohydantoin products from the corresponding starting E- or Z-N′-alkenyl urea, each of which may be formed from the same N-allyl precursor by stereodivergent alkene isomerization. The reaction, formally a nucleophilic substitution at an sp2 carbon atom, allows the direct regioselective incorporation of mono-, di-, tri-, and tetrasubstituted olefins at the α-carbon of amino acid derivatives. The initially formed 5-alkenyl iminohydantoins may be hydrolyzed and oxidatively deprotected to yield hydantoins and unsaturated α-quaternary amino acids.

Original languageEnglish
Pages (from-to)10750-10754
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number36
Early online date31 Jul 2017
DOIs
Publication statusPublished - 28 Aug 2017

Keywords

  • alkenes
  • amino acids
  • coupling reactions
  • hydantoin
  • urea

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