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

1 Citation (Scopus)

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

Fingerprint

Riboflavin
Isomerization
isomerization
Derivatives
riboflavin
Isomers
Energy Transfer
Thermodynamics
isomers
trienes
vitamins
editing
dienes
Photocatalysts
Scaffolds
Energy transfer
energy transfer
Irradiation
thermodynamics
irradiation

Keywords

  • retinal isomerization
  • molecular editing
  • regioselective isomerization

Cite this

Livingstone, Keith ; Tenberge, Marius ; Pape, Felix ; Daniliuc, Constantin G. ; Jamieson, Craig ; Gilmour, Ryan. / Photocatalytic E→Z Isomerization of β-Ionyl Derivatives. In: Organic Letters. 2019 ; Vol. 21, No. 23. pp. 9677-9680.
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Photocatalytic E→Z Isomerization of β-Ionyl Derivatives. / Livingstone, Keith; Tenberge, Marius; Pape, Felix; Daniliuc, Constantin G.; Jamieson, Craig; Gilmour, Ryan.

In: Organic Letters, Vol. 21, No. 23, 06.12.2019, p. 9677-9680.

Research output: Contribution to journalArticle

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T1 - Photocatalytic E→Z Isomerization of β-Ionyl Derivatives

AU - Livingstone, Keith

AU - Tenberge, Marius

AU - Pape, Felix

AU - Daniliuc, Constantin G.

AU - Jamieson, Craig

AU - Gilmour, Ryan

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AB - 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.

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