Synthesis, Structure, and Properties of β-Vinyl Ketone/Ester Functionalized AzaBODIPYs from FormylazaBODIPYs
Synthesis, Structure, and Properties of β-Vinyl Ketone/Ester Functionalized AzaBODIPYs from FormylazaBODIPYs
复制标题
甲酰基氮杂 BODIPY 的 β-乙烯基酮/酯功能化 AzaBODIPY 的合成、结构和性能
DOI：
10.1021/acsomega.7b00393
复制
发表时间：
2017-06-01
期刊：
影响因子：
4.1
通讯作者：
Jiao, Lijuan
中科院分区：
文献类型：
--
作者：
Wang, Jun;Wu, Yayang;Jiao, Lijuan
由于 azaBODIPY（氮杂二吡咯亚甲基的 BF2 络合物）在 650 nm 以上波长处具有强可调吸收带，并且此类染料在生物医学和材料科学中具有广泛的应用，因此非常需要对其进行后官能化。目前此类染料可用的后官能化方法仅限于 β-卤化（溴化或碘化）azaBODIPY 平台上的 Pd 催化偶联反应。在这项工作中，我们报告了一种新策略，基于我们之前开发的 β-甲酰基氮杂BODIPYs 和我们最近开发的 β-溴-β'-甲酰基氮杂BODIPYs 上的 Wittig 反应，用各种乙烯基酮和乙烯基酯对 azaBODIPY 发色团进行轻松的后官能化。我们的策略使用易于获得的起始材料和温和的反应条件。它与各种常见的磷叶立德（脂肪族、芳香族和酯取代的）高度相容。这些所得的含溴的β-乙烯基酮/酯官能化的azaBODIPY是潜在的光敏剂，并且可以通过偶联反应进一步官能化。一些所得的 azaBODIPY 上的酯基可以进一步水解，以达到所需的水溶性并与生物分子和固体表面缀合。
Postfunctionalization of azaBODIPY (the BF2 complex of azadipyrromethene) is highly desirable due to the strong tunable absorption bands at wavelengths above 650 nm and the wide-ranging applications of this class of dyes in biomedicine and materials science. Currently available postfunctionalization methods for this class of dyes have been limited to the Pd-catalyzed coupling reactions on β-halogenated (brominated or iodinated) azaBODIPY platforms. In this work, we report a new strategy for the facile postfunctionalization of the azaBODIPY chromophore with various vinyl ketone and vinyl esters based on a Wittig reaction on our previously developed β-formylazaBODIPYs and our recently developed β-bromo-β′-formylazaBODIPYs. Our strategy uses easily accessible starting materials and mild reaction conditions. It is highly compatible with various common phosphonium ylides (aliphatic, aromatic, and ester substituted ones). These resultant bromo-containing β-vinyl ketone/ester functionalized azaBODIPYs are potential photosensitizers and can be further functionalized via coupling reactions. The ester groups on some of these resultant azaBODIPYs can be further hydrolyzed to achieve the desired water solubility and conjugate with the biomolecule and solid surface.