Contra-thermodynamic E → Z isomerization of cinnamamides via selective energy transfer catalysis

Marc R. Becker; Tobias Morack; Jack Robertson; Jan B. Metternich; Christian Mück-Lichtenfeld; Constantin Daniliuc; Glenn A. Burley; Ryan Gilmour

doi:10.1016/j.tet.2020.131198

Contra-thermodynamic E → Z isomerization of cinnamamides via selective energy transfer catalysis

Marc R. Becker, Tobias Morack, Jack Robertson, Jan B. Metternich, Christian Mück-Lichtenfeld, Constantin Daniliuc, Glenn A. Burley, Ryan Gilmour

Pure And Applied Chemistry

Research output: Contribution to journal › Article

Abstract

A bio-inspired, photocatalytic E → Z isomerization of cinnamides is reported using inexpensive (−)-riboflavin (vitamin B2) under irradiation at λ = 402 nm. This operationally simple transformation is compatible with a range of amide derivatives including –NR2, –NHSO2R and N(Boc)2 (up to 99:1 Z:E). Selective energy transfer from the excited state photocatalyst to the starting E-isomer ensures that directionality is achieved: The analogous process with the Z-isomer is inefficient due to developing allylic strain causing chromophore deconjugation. This is supported by X-ray analysis and Stern-Volmer photo-quenching studies. Preliminary validation of the method in manipulating the conformation of a simple model Leu-enkephalin penta-peptide is disclosed via the incorporation of a cinnamamide-based amino acid.

Original language	English
Article number	131198
Number of pages	8
Journal	Tetrahedron
Early online date	4 May 2020
DOIs	https://doi.org/10.1016/j.tet.2020.131198
Publication status	E-pub ahead of print - 4 May 2020

Keywords

Alkene
catalysis
Energy transfer
Isomerization
Peptide

Access to Document

10.1016/j.tet.2020.131198

https://www.sciencedirect.com/journal/tetrahedron

Embargoed Document

Becker-etal-Tetrahedron-2020-Contra-thermodynamic-E-Z-isomerization-of-cinnamamides-via-selective-energy-transfer-catalysis
Accepted author manuscript, 1.19 MB
Licence: CC BY-NC-ND 4.0
Embargo ends: 4/05/21

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Projects

1 Active

Industrial Case Account 2016 | Robertson, Jack

Burley, G., Zagnoni, M. & Robertson, J.

EPSRC (Engineering and Physical Sciences Research Council)

1/10/16 → 1/02/21

Project: Research Studentship Case - Internally allocated

Cite this

Becker, M. R., Morack, T., Robertson, J., Metternich, J. B., Mück-Lichtenfeld, C., Daniliuc, C., Burley, G. A., & Gilmour, R. (2020). Contra-thermodynamic E → Z isomerization of cinnamamides via selective energy transfer catalysis. Tetrahedron, [131198]. https://doi.org/10.1016/j.tet.2020.131198

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abstract = "A bio-inspired, photocatalytic E → Z isomerization of cinnamides is reported using inexpensive (−)-riboflavin (vitamin B2) under irradiation at λ = 402 nm. This operationally simple transformation is compatible with a range of amide derivatives including –NR2, –NHSO2R and N(Boc)2 (up to 99:1 Z:E). Selective energy transfer from the excited state photocatalyst to the starting E-isomer ensures that directionality is achieved: The analogous process with the Z-isomer is inefficient due to developing allylic strain causing chromophore deconjugation. This is supported by X-ray analysis and Stern-Volmer photo-quenching studies. Preliminary validation of the method in manipulating the conformation of a simple model Leu-enkephalin penta-peptide is disclosed via the incorporation of a cinnamamide-based amino acid.",

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AU - Becker, Marc R.

AU - Morack, Tobias

AU - Robertson, Jack

AU - Metternich, Jan B.

AU - Mück-Lichtenfeld, Christian

AU - Daniliuc, Constantin

AU - Burley, Glenn A.

AU - Gilmour, Ryan

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AB - A bio-inspired, photocatalytic E → Z isomerization of cinnamides is reported using inexpensive (−)-riboflavin (vitamin B2) under irradiation at λ = 402 nm. This operationally simple transformation is compatible with a range of amide derivatives including –NR2, –NHSO2R and N(Boc)2 (up to 99:1 Z:E). Selective energy transfer from the excited state photocatalyst to the starting E-isomer ensures that directionality is achieved: The analogous process with the Z-isomer is inefficient due to developing allylic strain causing chromophore deconjugation. This is supported by X-ray analysis and Stern-Volmer photo-quenching studies. Preliminary validation of the method in manipulating the conformation of a simple model Leu-enkephalin penta-peptide is disclosed via the incorporation of a cinnamamide-based amino acid.

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KW - catalysis

KW - Energy transfer

KW - Isomerization

KW - Peptide

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