刘国凯副教授科研成果 | PT-CF₂H⁺BF₄⁻：告别光敏剂，一剂解锁三种模式二氟甲基化
2026-04-10 · 推荐产品 · 百灵威授权转载
在药物和农药分子中引入二氟甲基（CF₂H），能改善分子的代谢稳定性、脂溶性和生物利用度。也正因为如此，如何高效、可控地实现二氟甲基化，一直是氟化学和药物化学领域的研究重点。
但现有的亲电二氟甲基试剂，普遍存在稳定性差、反应活性低、结构难修饰等问题，而且大多只能作为二氟卡宾前体，反应模式比较单一。
针对这些局限，深圳大学刘国凯团队基于吩噁噻骨架，开发了一种新型亲电二氟甲基锍盐试剂——S-(二氟甲基)-吩噁噻硫鎓四氟硼酸盐 (PT-CF₂H⁺BF₄⁻)。吩噁噻的刚性环骨架及S/O原子间的电子相互作用赋予了该试剂独特的电子特性：较高的氧化还原电位（Ered = −0.88 V vs. Ag/AgCl）以及较低的S-CF₂H键解离能，在稳定性、反应模式与操作便捷性上实现了显著提升。
图1. PT-CF₂H⁺BF₄⁻ 的设计策略与核心优势
产品核心优势
●超高稳定性：结晶性粉末，对空气/湿气不敏感。
●一剂三用：可实现•CF₂H、+CF₂H、:CF₂H三种活性物种转化，覆盖自由基、亲电、卡宾等多种反应机制。
●无需光敏剂：可见光（365-395 nm）直接引发，无需外加光催化剂，体系更简单、成本更低。
●兼容性强：适用于光氧化还原催化、EDA介导的光诱导、光氧化还原/过渡金属协同催化、光诱导过渡金属催化、电催化等多种催化体系。
●平台型工具：为二氟甲基化新方法开发提供通用试剂。
应用实例
见图2。
图2. PT-CF₂H⁺BF₄⁻的应用实例
产品列表
二氟甲基锍盐试剂 品名 CAS 货号 S-(Difluoromethyl)phenoxathiinium tetrafluoroborate, 95%
S-(二氟甲基)-吩噁噻硫鎓四氟硼酸盐 3028056-12-1 9617870
光催化剂 品名 CAS 货号 Tris(2-phenylpyridine)iridium, 99%, for synthesis
三(2-苯基吡啶)合铱 94928-86-6 997766
Tris(2,2'-bipyridyl)ruthenium(II)chloride hexahydrate, 98%
三(2,2’-联吡啶基)氯化钌(II)六水合物 50525-27-4 102033
溶剂 品名 CAS 货号 Fluorobenzene, 99%, for synthesis
氟苯 462-06-6 948533
危化品 Dichloromethane, 99.9%, SuperDry, with molecular sieves, water≤30 ppm, J&KSeal
二氯甲烷 75-09-2 908525促
危化品 Ethyl acetate, 99.5%, SuperDry, Water≤50 ppm, J&KSeal
乙酸乙酯 141-78-6 954403促
危化品 Acetonitrile, 99.9%, SuperDry, with molecular sieves, water≤50 ppm, J&KSeal
乙腈 75-05-8 939631促
危化品
碱 品名 CAS 货号 Lithium hydroxide, 99%, anhydrous
氢氧化锂 1310-65-2 500019
危化品 Sodium hydride, for synthesis, 60%, dispersion in mineral oil
氢化钠 7646-69-7 961241
危化品 Potassium phosphate tribasic, 99%, reagent grade
磷酸三钾 7778-53-2 949522
Sodium bicarbonate, 99.5%, for analysis
碳酸氢钠 144-55-8 907280
耗材 品名 CAS 货号 Silica gel, 200-425 mesh
硅胶 112926-00-8 227599
Quantitative spotting capillary tubes, 1 μl, capacity error ±0.05 μl
定量点样毛细管 / 9219772
TLC silica gel plate (fluorescent indicator), GF254, layer thickness 0.2-0.25 mm, 100*100 mm, 80 pcs/pack
薄层色谱硅胶板(含荧光) / 983347
Magnetic stir bar, PTFE-coated, egg-shaped, A200(8-9mm*20mm), 5 pcs/pack
聚四氟乙烯磁力搅拌子,椭圆型 / 978702
More
参考文献
- Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent •CF₂H, CF₂H+ and :CF₂ reactivities, Sci. China Chem. 2024, 67(3), 953−962.
- Ready Synthesis of 3-Difluoromethylated Coumarins Enabled by Photosensitizer-Free Photoinduced Radical Difluoromethylation of Alkynoates, Chin. J. Org. Chem. 2025, 45, 1739−1746.
- Photocatalyst- and Oxidant-Free Photoinduced Radical Cascade for the Synthesis of Difluoromethylated Dihydroisoquinolones from N-Allylbenzamides with a Difluoromethyl Phenoxathiinium Salt, Eur. J. Org. Chem. 2025, 28, e202500214.
- Photocatalyst-Free Visible-Light Induced Radical Difluoromethylation/Cyclization Cascade Reaction for the Synthesis of Difluoromethylated Oxindoles with Difluoromethyl Phenoxathiinium Salt, Eur. J. Org. Chem. 2024, e202400948.
推荐阅读
有机氟化学——氟化物合成及转化常用产品，更有新型氟化试剂！
有机氟化合物合成通用试剂——二氟甲基(2-吡啶基)砜在药物领域的应用
有机氟化学——常用氟化试剂TMSCF3的应用及制备
S-(二氟甲基)-吩噁噻硫鎓四氟硼酸盐
| 品名 | CAS | 货号 |
|---|---|---|
| Tris(2-phenylpyridine)iridium, 99%, for synthesis 三(2-苯基吡啶)合铱 | 94928-86-6 | 997766 |
| Tris(2,2'-bipyridyl)ruthenium(II)chloride hexahydrate, 98% 三(2,2’-联吡啶基)氯化钌(II)六水合物 | 50525-27-4 | 102033 |
溶剂 品名 CAS 货号 Fluorobenzene, 99%, for synthesis
氟苯 462-06-6 948533
危化品 Dichloromethane, 99.9%, SuperDry, with molecular sieves, water≤30 ppm, J&KSeal
二氯甲烷 75-09-2 908525促
危化品 Ethyl acetate, 99.5%, SuperDry, Water≤50 ppm, J&KSeal
乙酸乙酯 141-78-6 954403促
危化品 Acetonitrile, 99.9%, SuperDry, with molecular sieves, water≤50 ppm, J&KSeal
乙腈 75-05-8 939631促
危化品
氟苯
危化品
二氯甲烷
危化品
乙酸乙酯
危化品
乙腈
危化品
碱 品名 CAS 货号 Lithium hydroxide, 99%, anhydrous
氢氧化锂 1310-65-2 500019
危化品 Sodium hydride, for synthesis, 60%, dispersion in mineral oil
氢化钠 7646-69-7 961241
危化品 Potassium phosphate tribasic, 99%, reagent grade
磷酸三钾 7778-53-2 949522
Sodium bicarbonate, 99.5%, for analysis
碳酸氢钠 144-55-8 907280
耗材 品名 CAS 货号 Silica gel, 200-425 mesh
硅胶 112926-00-8 227599
Quantitative spotting capillary tubes, 1 μl, capacity error ±0.05 μl
定量点样毛细管 / 9219772
TLC silica gel plate (fluorescent indicator), GF254, layer thickness 0.2-0.25 mm, 100*100 mm, 80 pcs/pack
薄层色谱硅胶板(含荧光) / 983347
Magnetic stir bar, PTFE-coated, egg-shaped, A200(8-9mm*20mm), 5 pcs/pack
聚四氟乙烯磁力搅拌子,椭圆型 / 978702
More
参考文献
- Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent •CF₂H, CF₂H+ and :CF₂ reactivities, Sci. China Chem. 2024, 67(3), 953−962.
- Ready Synthesis of 3-Difluoromethylated Coumarins Enabled by Photosensitizer-Free Photoinduced Radical Difluoromethylation of Alkynoates, Chin. J. Org. Chem. 2025, 45, 1739−1746.
- Photocatalyst- and Oxidant-Free Photoinduced Radical Cascade for the Synthesis of Difluoromethylated Dihydroisoquinolones from N-Allylbenzamides with a Difluoromethyl Phenoxathiinium Salt, Eur. J. Org. Chem. 2025, 28, e202500214.
- Photocatalyst-Free Visible-Light Induced Radical Difluoromethylation/Cyclization Cascade Reaction for the Synthesis of Difluoromethylated Oxindoles with Difluoromethyl Phenoxathiinium Salt, Eur. J. Org. Chem. 2024, e202400948.
推荐阅读
有机氟化学——氟化物合成及转化常用产品，更有新型氟化试剂！
有机氟化合物合成通用试剂——二氟甲基(2-吡啶基)砜在药物领域的应用
有机氟化学——常用氟化试剂TMSCF3的应用及制备
氢氧化锂
危化品
氢化钠
危化品
磷酸三钾
碳酸氢钠
| 品名 | CAS | 货号 |
|---|---|---|
| Silica gel, 200-425 mesh 硅胶 | 112926-00-8 | 227599 |
| Quantitative spotting capillary tubes, 1 μl, capacity error ±0.05 μl 定量点样毛细管 | / | 9219772 |
| TLC silica gel plate (fluorescent indicator), GF254, layer thickness 0.2-0.25 mm, 100*100 mm, 80 pcs/pack 薄层色谱硅胶板(含荧光) | / | 983347 |
| Magnetic stir bar, PTFE-coated, egg-shaped, A200(8-9mm*20mm), 5 pcs/pack 聚四氟乙烯磁力搅拌子,椭圆型 | / | 978702 |
参考文献
- Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent •CF₂H, CF₂H+ and :CF₂ reactivities, Sci. China Chem. 2024, 67(3), 953−962.
- Ready Synthesis of 3-Difluoromethylated Coumarins Enabled by Photosensitizer-Free Photoinduced Radical Difluoromethylation of Alkynoates, Chin. J. Org. Chem. 2025, 45, 1739−1746.
- Photocatalyst- and Oxidant-Free Photoinduced Radical Cascade for the Synthesis of Difluoromethylated Dihydroisoquinolones from N-Allylbenzamides with a Difluoromethyl Phenoxathiinium Salt, Eur. J. Org. Chem. 2025, 28, e202500214.
- Photocatalyst-Free Visible-Light Induced Radical Difluoromethylation/Cyclization Cascade Reaction for the Synthesis of Difluoromethylated Oxindoles with Difluoromethyl Phenoxathiinium Salt, Eur. J. Org. Chem. 2024, e202400948.
推荐阅读
有机氟化学——氟化物合成及转化常用产品，更有新型氟化试剂！有机氟化合物合成通用试剂——二氟甲基(2-吡啶基)砜在药物领域的应用
有机氟化学——常用氟化试剂TMSCF3的应用及制备
