Asymmetric and Geometry-Selective α-Alkenylation of α-Amino Acids

Hossay Abas, Josep Mas-Roselló, Mostafa Mahmoud Amer, Derek J. Durand, Robin R. Groleau, Natalie Fey, Jonathan Clayden

Research output: Contribution to journalArticlepeer-review

22 Citations (SciVal)


Both E- and Z-N′-alkenyl urea derivatives of imidazolidinones may be formed selectively from enantiopure α-amino acids. Generation of their enolate derivatives in the presence of K + and [18]crown-6 induces intramolecular migration of the alkenyl group from N′ to Cα with retention of double bond geometry. DFT calculations indicate a partially concerted substitution mechanism. Hydrolysis of the enantiopure products under acid conditions reveals quaternary α-alkenyl amino acids with stereodivergent control of both absolute configuration and double bond geometry.

Original languageEnglish
Pages (from-to)2418-2422
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number8
Publication statusPublished - 18 Feb 2019

Bibliographical note

Funding Information:
This work was supported by the ERC and EPSRC, the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1), Syngenta (CASE award to JM-R) and the Presidential Leadership Program of Egypt (scholarship to MMA).

Funding Information:
We used standard DFT calculations (see Supporting Information for full computational details) to probe the mechanism of reaction of E and Z-3a, as set out [for (E,2S)-3a] in Scheme 5. After deprotonation, the charge on the enolate oxygen is stabilized by coordination to [K+[18]c-6] to give E-1. Development of the energetically accessible syn-carbometallation intermediate E-2 is supported by chelation of the [K+[18]c-6] counterion. A transition state E-TS could

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • DFT calculations
  • quaternary amino acids
  • rearrangement
  • stereodivergence
  • α-alkenylation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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