Photocatalytic E→Z Isomerization of β-Ionyl Derivatives

Keith Livingstone, Marius Tenberge, Felix Pape, Constantin G. Daniliuc, Craig Jamieson, Ryan Gilmour

Research output: Contribution to journalArticle

7 Citations (Scopus)
1 Downloads (Pure)

Abstract

An operationally simple E → Z isomerization of activated dienes, based on the β-ionyl motif intrinsic to retinal, is reported using inexpensive (−)-riboflavin (vitamin B2) under irradiation at 402 nm. Selective energy transfer from photoexcited (−)-riboflavin to the starting E-isomer enables geometrical isomerization. Since the analogous process with the Z-isomer is inefficient, microscopic reversibility is circumvented, thereby enabling a directional isomerization to generate the contra-thermodynamic product (up to 99% yield, up to 99:1 Z/E). Prudent choice of photocatalyst enables chemoselective isomerization to be achieved in both inter- and intramolecular systems. The principles established from this study, together with a molecular editing approach, have facilitated the development of a regioselective isomerization of a truncated triene based on the retinal scaffold.
Original languageEnglish
Pages (from-to)9677-9680
Number of pages4
JournalOrganic Letters
Volume21
Issue number23
Early online date20 Nov 2019
DOIs
Publication statusPublished - 6 Dec 2019

Keywords

  • retinal isomerization
  • molecular editing
  • regioselective isomerization

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