配体-金属电荷转移驱动的光促金属催化芳基羧酸脱羧转化

doi:10.6023/cjoc202601011

摘要/Abstract

羧酸是一类来源丰富、结构多样、性质稳定、价格友好的化学物质, 是仅次于胺的第二大类商业可得有机分子砌块. 发展光催化自由基脱羧反应, 将羧酸转化为各类高附加值化合物, 是过去十余年有机化学的热门研究领域之一. 到目前为止, 光催化烷基羧酸的脱羧转化研究已经取得较大进展, 而芳基羧酸相关研究的进展较为迟缓, 主要原因是芳基羧基自由基脱羧较慢, 后续的芳基自由基活性很高, 存在诸多竞争反应. 在过去五年, 配体-金属电荷转移(LMCT)驱动的光促金属催化/介导的芳基羧酸(盐)脱羧转化研究已取得一些进展, 包括光促铜催化/介导的卤化、羟化、磺酰亚胺化、硼化、卤磺酰化、噻蒽化、烯丙基化、硫醚化和氢化, 以及光促铁催化的硫醚化和溴化, 但是仍需要通过巧妙设计、调控反应参数, 发展更多的脱羧反应类型, 比如将配体-金属电荷转移与过渡金属催化相结合, 实现芳基羧酸的脱羧交叉偶联反应.

关键词: 配体-金属电荷转移驱动, 光促, 金属催化, 芳基羧酸, 脱羧转化, 自由基反应

Carboxylic acids are a class of chemicals with abundant sources, structural diversity, stability, and cost- effectiveness, representing the second largest class of commercially available organic building blocks after amines. The past decade has witnessed the rapid development of photoinduced radical decarboxylative transformation of alkyl carboxylic acids. However, the progress in the decarboxylative transformation of aryl carboxylic acids is slow, mianly due to the relatively reluctant decarboxylation of O-centered aryl carboxylate radicals and the subsequent very reactive aryl radicals, suffering severe competitive pathways. In the latest five years, ligand-to-metal charge transfer (LMCT)-driven photoinduced metal- catalyzed/mediated decarboxylative transformation of aryl carboxylic acids (carboxylates) has gained some achievements, such as copper-catalyzed/mediated halogenation, hydroxylation, sulfoximination, borylation, halosulfonylation, thianthrenation, allylation, thiolation and hydrogenation, iron-catalyzed thiolation and bromination. Further development is highly expected to realize new types of reactions through smart design and control of reaction conditions. For instance, the merger of LMCT and transition metal catalysis might provide an opportunity to achieve the decarboxylative cross-coupling of aryl carboxylic acids.

Key words: ligand-to-metal charge transfer (LMCT)-driven, photoinduced, metal catalysis, aryl carboxylic acid, decarboxylative transformation, radical reaction

引用此文

吉伟文, 金健. 配体-金属电荷转移驱动的光促金属催化芳基羧酸脱羧转化[J]. 有机化学, 2026, 46(4): 1320-1329.

Weiwen Ji, Jian Jin. Ligand-to-Metal Charge Transfer-Driven Photoinduced Metal-Catalyzed Decarboxylative Transformation of Aryl Carboxylic Acids[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1320-1329.

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图/表 15

图式1. 光催化芳基羧酸脱羧转化

Scheme 1. Photocatalytic decarboxylative transformation of aryl carboxylic acids

图式2. 光促铜介导芳基羧酸的脱羧氟化

Scheme 2. Photoinduced copper-mediated decarboxylative fluorination

图式3. 光促铜介导芳基羧酸的脱羧羟化

Scheme 3. Photoinduced copper-mediated decarboxylative hydroxylation

图式4. 光促铜介导芳基羧酸的脱羧磺酰亚胺化

Scheme 4. Photoinduced copper-mediated decarboxylative sulfoximination

图式5. 光促铜催化芳基羧酸的脱羧碘化或溴化

Scheme 5. Photoinduced copper-catalyzed decarboxylative iodination/bromination

图式6. 光促铜介导芳基羧酸的脱羧氯化或氟化

Scheme 6. Photoinduced copper-catalyzed decarboxylative chlorination/fluorination

图式7. 光促铜催化芳基羧酸的脱羧硼化

Scheme 7. Photoinduced copper-catalyzed decarboxylative bor- ylation

图式8. 光促铜催化芳基羧酸的脱羧氯或氟磺酰化

Scheme 8. Photoinduced copper-catalyzed decarboxylative chloro/fluorosulfonylation

图式9. 光促铜介导芳基羧酸的脱羧噻蒽化

Scheme 9. Photoinduced copper-mediated decarboxylative thianthrenation

图式10. 光促铜介导芳基羧酸的脱羧烯丙基化、硫醚化或溴化

Scheme 10. Photoinduced copper-mediated decarboxylative all- ylation/thiolation/bromination

图式11. 光促铜介导芳基羧酸的脱羧氢化

Scheme 11. Photoinduced copper-mediated decarboxylative hydrogenation

图式12. 光促铜介导芳基羧酸的脱羧氟-18化

Scheme 12. Photoinduced copper-mediated decarboxylative 18F- fluorination

图式13. 光促铁催化芳基羧酸的脱羧硫醚化

Scheme 13. Photoinduced iron-catalyzed decarboxylative thiolation

图式14. 光促铁催化芳基羧酸的脱羧溴化

Scheme 14. Photoinduced iron-catalyzed decarboxylative bromination

图式15. 总结与展望

Scheme 15. Summary and outlook

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