Thieno[3,2-b]pyridin-5(4H)-ones 의 합성과 광화학적특성

Abstract

Molecular fluorescence is a rapidly growing research field, which has significant applications in physical, chemical, material, and biomedical sciences. In our continued efforts to construct a small molecular library of natural product-inspired fused heterocylic ring systems, thieno[3,2-b]pyridine-5(4H)-one has been recognized as a novel fluorescent scaffold. In this presentation, we demonstrate the synthesis of highly fluorescent thieno[3,2-b]pyridine-5(4H)-one derivatives and the photophysical properties of the resulting products. The chemical synthesis of these novel fluorophores employs a series of subsequent reactions employing the Suzuki-Miyaura cross-coupling reaction, and a regioselective aza-[3 + 3] cycloaddition reaction of 3-aminothiophenes with alpha,beta-unsaturated carboxylic acids promoted by BOP ((benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate). The structure-property relationship study of this novel fluorescent scaffold revealed that the introduction of a specific functional group to the thieno[3,2-b]pyridine-5(4H)-one scaffold enables the photophysical properties to be finely tuned. Consequently, significant hypsochromic and bathochromic shifts with large Stokes shifts up to 7672 cm-1 were observed and high quantum yields up to 99% were obtained in dichloromethane. The inherent ease of chemical modification of this fluorescent scaffold would bestow a tailor-made function into a molecule of choice.[1] Valeur, B. Berberan-Santos, M. N., Molecular Fluorescence, Second Edition. Wiley: 2012.[2] Lavis, L. D. Raines, R. T., ACS Chem. Biol. 2008, 3, 142-155.[3] Lavis, L. D. Raines, R. T., ACS Chem. Biol. 2014, 9, 855-866.