钟为慧教授科研成果|告别盲目筛选！18种PNN配体，让不对称氢化少走弯路
2026-07-21 · 推荐产品 · 百灵威授权转载
不对称氢化是构建手性醇、手性胺等药物及精细化学品关键中间体最高效、最原子经济的方法之一。配体的设计直接决定了催化体系的活性和对映选择性。
浙江工业大学钟为慧教授开发出一系列手性二茂铁骨架PNN三齿配体，涵盖f-Diaphos、咪唑/苯并咪唑PNN等经典配体系列，适用于Ir、Mn、Ru等多种过渡金属催化的不对称氢化、动态动力学拆分（DKR）及借氢反应，为您的手性合成提供“即用型”解决方案。
核心优势：
- 性能卓越，文献佐证：f-Diaphos/Ir体系在芳基烷基酮的不对称氢化中，对映选择性高达99.4% ee，转化数（TON）可达100,000[1,2] ；在非邻位取代2-吡啶基芳基酮氢化中同样表现优异[3]。
- 挑战底物，轻松应对：成功应用于α-氟/氯-β-酮酰胺/酯的动态动力学拆分（DKR）[1,4]，以及非邻位取代2-吡啶基芳基酮 [3]、2-咪唑基芳基/烷基酮等杂环酮底物的高选择性氢化。
- 金属兼容，体系丰富：除铱催化体系外，相关咪唑类PNN配体还可与锰配位，实现二苯甲酮、α,β-不饱和酮等底物的不对称氢化，对映选择性高达>99% ee [5]，拓展了廉价金属在不对称合成中的应用。
- 可放大，可负载：相关催化体系已实现克级规模放大，负载型f-Diaphos配体更可应用于连续流反应，在百克级规模下稳定运行，展现出工业化潜力 [2]。
百灵威稳定供应一系列手性二茂铁骨架PNN三齿配体及相关配套产品，助力不对称合成。
产品清单
f-Diaphos系列配体
| 品名 | CAS | 货号 |
|---|---|---|
| (1R)-1-(Diphenylphosphino)-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(2,4,6-trimethylphenyl)sulfonyl]amino]cyclohexyl]amino]ethyl]ferrocene, 98%, ee≥99% (1R)-1-(二苯基膦基)-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(2,4,6-三甲基苯基)磺酰基]氨基]环己基]氨基]乙基]二茂铁 | 2241798-02-5 | 9743081 |
| (1R)-1-(Diphenylphosphino)-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(4-methylphenyl)sulfonyl]amino]cyclohexyl]amino]ethyl]ferrocene, 98%, ee≥99% (1R)-1-(二苯基膦基)-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(4-甲基苯基)磺酰基]氨基]环己基]氨基]乙基]二茂铁 | 2197989-00-5 | 9743082 |
| (1R)-1-[Bis[[3,5-bis(1,1-dimethylethyl)phenyl]phosphino]-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(4-methylphenyl)sulfonyl]amino]cyclohexyl]amino]ethyl]ferrocene, 98%, ee≥99% (1R)-1-[双[[3,5-双(1,1-二甲基乙基)苯基]膦基]-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(4-甲基苯基)磺酰基]氨基]环己基]氨基]乙基]二茂铁 | 2241798-10-5 | 9743083 |
| (1R)-1-[Bis(3,5-dimethylphenyl)phosphino]-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(2,4,6-trimethylphenyl)sulfonyl]amino]cyclohexyl]amino]ethyl]ferrocene, 98%, ee≥99% (1R)-1-[双(3,5-二甲基苯基)膦基]-2-[(1R)-1-[[[[(1R,2R)-2-[[[[(2,4,6-三甲基苯基)磺酰基]氨基]环己基]氨基]乙基]二茂铁 | 2241798-08-1 | 9743095 |
| (1S)-1-(Diphenylphosphino)-2-[(1S)-1-[[[[(1S,2S)-2-[[[[(4-methylphenyl)sulfonyl]amino]cyclohexyl]amino]ethyl]ferrocene, 98%, ee≥99% (1S)-1-(二苯基膦基)-2-[(1S)-1-[[[[(1S,2S)-2-[[[[(4-甲基苯基)磺酰基]氨基]环己基]氨基]乙基]二茂铁 | 2241798-15-0 | 9743096 |
| (1S)-1-(Diphenylphosphino)-2-[(1S)-1-[[[[(1S,2S)-2-[[[[(2,4,6-trimethylphenyl)sulfonyl]amino]cyclohexyl]amino]ethyl]ferrocene, 98%, ee≥99% (1S)-1-(二苯基膦基)-2-[(1S)-1-[[[[(1S,2S)-2-[[[[(2,4,6-三甲基苯基)磺酰基]氨基]环己基]氨基]乙基]二茂铁 | 2368926-14-9 | 9743097 |
| (1S)-1-[Bis[[3,5-bis(1,1-dimethylethyl)phenyl]phosphino]-2-[(1S)-1-[[[[(1S,2S)-2-[[[[(4-methylphenyl)sulfonyl]amino]cyclohexyl]amino]ethyl]ferrocene, 98%, ee≥99% (1S)-1-[双[[3,5-双(1,1-二甲基乙基)苯基]膦基]-2-[(1S,1S,2S)-2-[[[[(4-甲基苯基)磺酰基]氨基]环己基]氨基]乙基]二茂铁 | 2368926-18-3 | 9743098 |
咪唑/苯并咪唑系列配体
| 品名 | CAS | 货号 |
|---|---|---|
| (1R)-1-(Diphenylphosphino)-2-[(1R)-1-[[[[(1-methyl-1H-benzimidazol-2-yl)methyl]amino]ethyl]ferrocene, 98%, ee≥99% (1R)-1-(二苯基膦基)-2-[(1R)-1-[[[[(1-甲基-1H-苯并咪唑-2-基)甲基]氨基]乙基]二茂铁 | 2375958-02-2 | 9743099 |
| (1S)-1-(Diphenylphosphino)-2-[(1S)-1-[[[[(1-methyl-1H-benzimidazol-2-yl)methyl]amino]ethyl]ferrocene, 98%, ee≥99% (1S)-1-(二苯基膦基)-2-[(1S)-1-[[[[(1-甲基-1H-苯并咪唑-2-基)甲基]氨基]乙基]二茂铁 | 2409181-81-1 | 9743100 |
| (1S)-1-(Diphenylphosphino)-2-[(1S)-1-[[[[[[1-(phenylmethyl)-1H-benzimidazol-2-yl]methyl]amino]ethyl]ferrocene, 98%, ee≥99% (1S)-1-(二苯基膦基)-2-[(1S)-1-[[[[[[1-(苯基甲基)-1H-苯并咪唑-2-基]甲基]氨基]乙基]二茂铁 | 2375957-97-2 | 9743101 |
| (2S)-1-[(1S)-1-[[(E)-[[[[1-[[2,6-Bis(1-methylethyl)phenyl]-1H-benzimidazol-2-yl]methylene]amino]ethyl]-2-(diphenylphosphino)ferrocene, 98%, ee≥99% (2S)-1-[(1S)-1-[[(E)-[[[[1-[[2,6-双(1-甲基乙基)苯基]-1H-苯并咪唑-2-基]亚甲基]氨基]乙基]-2-(二苯基膦基)二茂铁 | 2346611-36-5 | 9743102 |
| (2R)-1-[(1R)-1-[[(E)-[[[[1-[[2,6-Bis(1-methylethyl)phenyl]-1H-benzimidazol-2-yl]methylene]amino]ethyl]-2-(diphenylphosphino)ferrocene, 98%, ee≥99% (2R)-1-[(1R)-1-[[(E)-[[[[1-[[2,6-双(1-甲基乙基)苯基]-1H-苯并咪唑-2-基]亚甲基]氨基]乙基]-2-(二苯基膦基)二茂铁 | 2346611-43-4 | 9743103 |
| (1S)-1-[Bis(3,5-dimethylphenyl)phosphino]-2-[(1S)-1-[[[[[[1-(phenylmethyl)-1H-benzimidazol-2-yl]methyl]amino]ethyl]ferrocene, 98%, ee≥99% (1S)-1-[双(3,5-二甲基苯基)膦基]-2-[(1S)-1-[[[[1-(苯基甲基)-1H-苯并咪唑-2-基]甲基]氨基]乙基]二茂铁 | 2375958-00-0 | 9743104 |
其他二茂铁配体
| 品名 | CAS | 货号 |
|---|---|---|
| (1S)-1-(Diphenylphosphino)-2-[(1S)-1-[[methyl[[(11aR)-10,11,12,13-tetrahydrodiindeno[[7,1-de:1′,7′-fg][1,3,2]dioxaphosphocin-5-yl]amino]ethyl]ferrocene, 98%, ee≥99% (1S)-1-(二苯基膦基)-2-[(1S”-1-[[甲基[[(11aR)-10,11,12,13-四氢二茚并[[7,1-de:1′,7′-fg][1,3,2]二氧膦-5-基]氨基]乙基]二茂铁 | 2775428-44-7 | 9743105 |
| (2R)-1-[(1R)-1-[[[[[[(2,4,6-trimethyl)benzoyl]amino]thioxomethyl]amino]ethyl]-1′,2-bis(diphenylphosphino)ferrocene, 98%, ee≥99% (2R)-1-[(1R)-1-[[[[[[(2,4,6-三甲基)苯甲酰基]氨基]硫氧甲基]氨基]乙基]-1’,2-双(二苯基膦基)二茂铁 | 2907054-15-1 | 9743106 |
| (2R)-1-[(1R)-1-[[[[[[(3,5-dimethyl)benzoyl] amino]thioxomethyl] methylamino]ethyl]-1′,2-bis(diphenylphosphino)ferrocene, 98%, ee≥99% (2R)-1-[(1R)-1-[[[[[[(3,5-二甲基)苯甲酰基]氨基]硫氧甲基]甲基氨基]乙基]-1′,2-双(二苯基膦基)二茂铁 | 2907054-07-1 | 9743110 |
| (2R)-1-[(1R)-1-[[[[[[(3,5-di-tert-butyl)benzoyl] amino]thioxomethyl] methylamino]ethyl]-1′,2-bis(diphenylphosphino)ferrocene, 98%, ee≥99% (2R)-1-[(1R)-1-[[[[[[(3,5-二叔丁基)苯甲酰基]氨基]硫氧甲基]甲基氨基]乙基]-1′,2-双(二苯基膦基)二茂铁 | 2907054-05-9 | 9743108 |
| (2R)-1-[(1R)-1-[[[[[[(2,4,6-trimethyl)benzoyl]amino]thioxomethyl] methylamino]ethyl]-1′,2-bis(di(3,5-di-methyl)phenylphosphino)ferrocene, 98%, ee≥99% (2R)-1-[(1R)-1-[[[[(2,4,6-三甲基)苯甲酰基]氨基]硫氧甲基]甲基氨基]乙基]-1′,2-双(二(3,5-二甲基)苯基膦基)二茂铁 | 2907054-17-3 | 9743109 |
金属前体
| 品名 | CAS | 货号 |
|---|---|---|
| Chloro(1,5-cyclooctadiene)iridium(I) dimer, 98% 1,5-环辛二烯氯化铱(I)二聚体 | 12112-67-3 | 192969 |
| Manganese pentacarbonyl bromide, 97% 五羰基溴化锰 | 14516-54-2 | 139902 |
通用溶剂
| 品名 | CAS | 货号 |
|---|---|---|
| Ethanol, 99.5%, SuperDry, with molecular sieves, Water≤50 ppm, J&KSeal 乙醇 | 64-17-5 | 922424促 危化品 |
| 1,4-Dioxane, 99.5%, SuperDry, with molecular sieves, stabilized with BHT, J&Kseal, water≤50 ppm 1,4-二氧六环 | 123-91-1 | 972869促 危化品 |
| Ethyl acetate, 99.9%, SuperDry, with molecular sieves, Water≤50 ppm, J&KSeal 乙酸乙酯 | 141-78-6 | 920352促 危化品 |
| Isopropanol, 99.5%, SuperDry, with molecular sieves, Water≤50 ppm, J&KSeal 异丙醇 | 67-63-0 | 919270促 危化品 |
耗材
| 品名 | CAS | 货号 |
|---|---|---|
| Quantitative spotting capillary tubes, 1 μl, capacity error ±0.05 μl 定量点样毛细管 | / | 9219772 |
| HPTLC silica gel plate (NaAc) (fluorescent indicator: no), 2% NaAc, 200*100 mm, layer thickness: 0.2-0.25 mm, particle size: 5-20 μm 高效薄层层析硅胶板(乙酸钠)(不含荧光) | / | 2750251 |
| Transfer pipets, 3 ml, 160 mm, PE, capacity 7.5 ml, unsterile 吸管 | / | 989082 |
| 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
- Iridium-Catalyzed Asymmetric Hydrogenation of Aryl α-Chloro-β-Keto Esters and Aryl Alkyl Ketones, Org. Lett., 2026, 28(14), 4531–4536.
- Development of Heterogeneous P-N-N Tridentate Ligand for Iridium-Catalyzed Asymmetric Hydrogenation of Ketones in Batch and Flow, Green Chem., 2025, 27, 3684–3692.
- Highly Enantioselective Hydrogenation of Non-ortho-Substituted 2-Pyridyl Aryl Ketones via Iridium-f-Diaphos Catalysis, Org. Lett., 2019, 21(14), 5392–5396.
- Asymmetric Hydrogenation of α-F-β-ketone Amides (Esters) via Ir/f-Diaphos Catalyzed Dynamic Kinetic Resolution, Org. Chem. Front., 2024, 11(8), 2201–2207.
- Highly Enantioselective Synthesis of Chiral Benzhydrols via Manganese Catalyzed Asymmetric Hydrogenation of Unsymmetrical Benzophenones using an Imidazole-Based Chiral PNN Tridentate Ligand, Org. Lett., 2019, 21(11), 3937–3941.
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