Foldamer-mediated remote stereocontrol: >1,60 asymmetric induction

Liam Byrne, Jordi Solà, Thomas Boddaert, Tommaso Marcelli, Ralph W. Adams, Gareth A. Morris, Jonathan Clayden*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

78 Citations (Scopus)

Abstract

An N-terminal L-α-methylvaline dimer induces complete conformational control over the screw sense of an otherwise achiral helical peptide foldamer formed from the achiral quaternary amino acids Aib and Ac6c. The persistent right-handed screw-sense preference of the helix enables remote reactive sites to fall under the influence of the terminal chiral residues, and permits diastereoselective reactions such as alkene hydrogenation or iminium ion addition to take place with 1,16-, 1,31-, 1,46- and even 1,61-asymmetric induction. Stereochemical information may be communicated in this way over distances of up to 4 nm. Reaction at a distance: By inducing a quantitative, persistent preference for right-handed helicity, chirality at one end of an otherwise achiral helical molecule is able to control the stereoselectivity of reactions at sites located up to 60 bonds away, shattering previous records for remote stereochemical control.

Original languageEnglish
Pages (from-to)151-155
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number1
Early online date8 Nov 2013
DOIs
Publication statusPublished - 3 Jan 2014

Keywords

  • acyliminium ions
  • asymmetric induction
  • helical molecules
  • peptides
  • remote stereocontrol

Fingerprint Dive into the research topics of 'Foldamer-mediated remote stereocontrol: >1,60 asymmetric induction'. Together they form a unique fingerprint.

Cite this