铁盐催化杂环化合物C-H芳基化

Heterobiaryl compounds represent a predominant structural motif in organic materials, biologically active substances, as well as drug molecules. Transition metal-catalyzed direct arylation opens a new convenient way for aryl-heteroaromatic compounds， while，the catalysts are predominated by heavy metals such as Pd、Cu。 products are often polluted by these heavy metals， and activated N-H often need to be protected。We found that iron salts could catalyze the direct C-H arylation of pyrrole without the protection of N-H; in the presence of an oxidant, simple iron salts could catalyze the direct aylation of benzoquinone and pyridine under room temperature. Based on these results, we continue to study iron-catalyzed arylation of other heteroaromatic compounds, such as indoles and bases. Iron salts-catalyzed arylation of protected or unprotected indole will be studied, and many aryl-heteroaryl or heteroaryl-heteroaryl compounds will be synthesized using this method. The direct arylation of purines and pyrimidines will also be studied. besides single base arylation, the consequent arylation of two bases, or base and fluorophores will be further studied.

芳基-芳杂环结构广泛存在于有机材料、生物活性物质、以及药物分子中。过渡金属催化杂环C-H直接芳基化是合成芳基化杂环化合物的便捷途径。直接芳基化的催化剂主要依赖于Pd、Cu等重金属，易造成重金属残留，而且活性N-H往往需要保护。我们研究发现铁盐能催化吡咯C-H直接选择性芳基化，N-H不需要保护；在氧化剂存在下，简单铁盐能在室温催化苯醌及吡啶的高效芳基化。以此为基础，拟继续对其它杂环化合物，如吲哚、碱基的直接芳基化展开深入研究，建立铁盐催化杂环C-H直接芳基化的绿色新方法。研究N-H游离或保护的吲哚C2选择性芳基化，合成多个芳基吲哚、芳杂环-吲哚化合物。研究有活性N-H存在的单个嘌呤及嘧啶类碱基的选择性芳基化，进一步考察多个碱基以及碱基与其它荧光团的连续芳基化。

碳氢化合物是制备复杂有机分子的最重要来源。因此，研究碳氢化合物的直接功能化具有重要的意义。本项目主要研究了一些简单、廉价催化体系或无催化剂的化学反应。首先实现了简单铜盐催化的芳基C-H选择性膦化；铜盐催化丙二胺与苯乙酮生成不对称吡啶。首次报道了烯卤及富电子的卤代五元杂环化合物的无金属磺化，生成烯基砜及杂环砜。发展了一些碘盐催化醛氧化制备酰胺的反应。在本项基金的支持下，已发表SCI收录论文15篇，引用次数120多次。