Synthesis and photophysical properties of charge-transfer based pyrimidine-derived ∝-amino acids

Songsri, S., Harkiss, A. H. and Sutherland, A. (2023) Synthesis and photophysical properties of charge-transfer based pyrimidine-derived ∝-amino acids. Journal of Organic Chemistry, 88(18), pp. 13214-13224. (doi: 10.1021/acs.joc.3c01437) (PMID:37621156) (PMCID:PMC10507667)

Abstract

The four-step synthesis of fluorescent pyrimidine-derived α-amino acids from an l-aspartic acid derivative is described. The key synthetic steps involved preparation of ynone intermediates via the reaction of alkynyl lithium salts with a Weinreb amide, followed by an ytterbium-catalyzed heterocyclization reaction with amidines. Variation of substituents at the C2- and C4-position of the pyrimidine ring allowed tuning of the photoluminescent properties of the α-amino acids. This revealed that a combination of highly conjugated or electron-rich aryl substituents with the π-deficient pyrimidine motif resulted in fluorophores with the highest quantum yields and overall brightness. Further analysis of the most fluorogenic α-amino acid demonstrated solvatochromism and sensitivity to pH.

• Item Type: Articles
• Additional Information: Financial support from the Royal Thai Government (studentship to S.S.), EPSRC (studentship to A.H.H, EP/K503058/1) and the University of Glasgow is gratefully acknowledged.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sutherland, Professor Andrew and Harkiss, Dr Alexander and Songsri, Sineenard
• Authors: Songsri, S., Harkiss, A. H., and Sutherland, A.
• College/School: College of Science and Engineering > School of Chemistry; College of Science and Engineering
• Journal Name: Journal of Organic Chemistry
• Publisher: American Chemical Society
• ISSN: 0022-3263
• ISSN (Online): 1520-6904
• Published Online: 24 August 2023
• Copyright Holders: Copyright © 2023 The Authors
• First Published: First published in Journal of Organic Chemistry 88(18): 13214–13224
• Publisher Policy: Reproduced under a Creative Commons license

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
190490		Engineering and Physical Sciences Doctoral Training Grant 2012-16	Mary Beth Kneafsey	Engineering and Physical Sciences Research Council (EPSRC)	EP/K503058/1	Research and Innovation Services