From one to two quaternary centers: ester or nitrile α-alkylation applied to bioactive alkaloids

Nicholas Voûte, Andrew Neal, Federico Medda, Craig A. Johnston, Alexandra M. Z. Slawin, Nicholas J. Westwood

Research output: Contribution to journalArticlepeer-review

Abstract

The synthesis of all-carbon quaternary centers remains a challenge. Here we describe studies on the formation of two adjacent all-carbon quaternary centers in the context of the planned synthesis of the bioactive natural products perophoramidine and the communesins. In one approach the key step involves ester-alkylation using either allyl bromide or formaldehyde as the electrophile. An unexpected rapid auto-oxidation reaction during the synthesis of the alkylation substrates limited the scalability of this approach. In a second route, alkylation of a nitrile-containing precursor was planned. The use of the TosMIC reagent on a complex substrate gave the nitrile for alkylation. The assignment of the relative stereochemistry of the products was done through the extensive use of small molecule X-ray crystallography.
Original languageEnglish
JournalTetrahedron
VolumeIn press
Early online date8 Nov 2018
DOIs
Publication statusE-pub ahead of print - 8 Nov 2018

Keywords

  • Dehaloperophoramidine
  • Diastereoselective
  • Quaternary
  • Stereocenter

Fingerprint

Dive into the research topics of 'From one to two quaternary centers: ester or nitrile α-alkylation applied to bioactive alkaloids'. Together they form a unique fingerprint.

Cite this