铁系金属催化烯烃不对称氢化反应的研究进展

doi:10.6023/cjoc202602021

摘要/Abstract

过渡金属催化前手性烯烃不对称氢化反应是构建手性化合物的重要方法之一, 因操作简便、后处理容易及原子经济性高等特点而备受关注. 该反应主要依赖钌、铑、铱及钯等贵金属催化体系, 然而这些金属资源有限、成本高昂, 且存在潜在环境风险. 为此, 过去数十年间, 研究者致力于发展以铁、钴和镍为代表的地球储量高、低毒/无毒且环境友好的廉价铁系金属催化体系, 并在不对称氢化领域取得了一系列重要突破. 简要评述了近年来铁系金属铁、钴及镍催化烯烃(C=C)不对称氢化反应的研究进展, 深入分析了该类催化体系在底物适用范围、催化效率与选择性等方面的优势与不足. 相关研究尽管已取得显著进展, 但仍面临诸多挑战, 包括反应机理尚不明晰和高效手性配体匮乏等. 未来亟需开发结构新颖、易于合成的手性配体, 并探索更具普适性的催化体系.

关键词: 不对称氢化, 丰产金属, 烯烃, 手性化合物, 立体选择性

Transition metal-catalyzed asymmetric hydrogenation of prochiral alkenes is an important method for the construction of chiral compounds, and has garnered great attention due to its operational simplicity, ease of work-up, and high atom economy. It mainly relied on noble metal catalytic systems such as ruthenium, rhodium, iridium, and palladium. However, these metals suffer from limited resources, high costs, and potential environmental risks. Therefore, over the past few decades, researchers have focused on the development of catalytic systems based on earth-abundant, low- or non-toxic, and environmentally friendly iron-group metals, including iron, cobalt, and nickel. Significant breakthroughs have been achieved in the field of asymmetric hydrogenation using these metals. The recent progress in iron-group metal (Fe, Co, Ni)-catalyzed asymmetric hydrogenation of alkenes (C=C) is briefly reviewed, and the in-depth analysis of the advantages and limitations of these catalytic systems in terms of substrate scope, catalytic efficiency, and selectivity is provided. Although remarkable progress has been made, the field still faces some challenges, including unclear reaction mechanisms and a lack of efficient chiral ligands. Future efforts should focus on the development of new, easily accessible chiral ligands and exploring more universal catalytic systems.

Key words: asymmetric hydrogenation, earth-abundant transition metal, olefin, chiral compound, stereoselectivity

引用此文

余品科, 刘海阳, 肖帆, 董秀琴. 铁系金属催化烯烃不对称氢化反应的研究进展[J]. 有机化学, 2026, 46(7): 2622-2643.

Pin-Ke Yu, Hai-Yang Liu, Fan Xiao, Xiu-Qin Dong. Recent Progress on Iron-Group Metal-Catalyzed Asymmetric Hydrogenation of Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2622-2643.

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图/表 45

图式1. 手性(ACNC)Fe配合物在烯烃不对称氢化中的应用

Scheme 1. Application of chiral (ACNC)Fe complexes in asymmetric hydrogenation of olefins

图式2. 铁/噁唑啉亚胺基喹啉催化烯烃的不对称氢化

Scheme 2. Fe/oxazoline-iminoquinoline-catalyzed asymmetric hydrogenation of olefins

图式3. 双亚胺基吡啶钴配合物的合成及其在烯烃不对称氢化中的应用

Scheme 3. Synthesis of pyridine bisimino cobalt(II) complex and its application in asymmetric hydrogenation of olefins

图式4. 钴/手性双膦配体催化2-乙酰氨基丙烯酸酯、氨基酸及烯酰胺衍生物的不对称氢化反应

Scheme 4. Co/chiral bisphosphine ligand-catalyzed asymmetric hydrogenation of 2-acetamidoacrylates, amino acid derivatives, and enamide derivatives

图式5. 双(亚胺基)吡啶钴催化的环状烯烃的不对称氢化反应

Scheme 5. Asymmetric hydrogenation of cycloalkenes catalyzed by Co(II)/(diimino)pyridine

图式6. Co/(R,R)-Ph-BPE催化不对称氢化合成左乙拉西坦

Scheme 6. Co/(R,R)-Ph-BPE-catalyzed asymmetric hydrogenation for the synthesis of levotetrahydropyridine

图式7. 钴催化α,β-不饱和羧酸的不对称氢化反应

Scheme 7. Co-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acids

图式8. 钴催化不对称氢化合成手性二硼化合物

Scheme 8. Synthesis of chiral diboron compounds via Co-catalyzed asymmetric hydrogenation

图式9. 钴催化烯酰胺的不对称氢化反应

Scheme 9. Co-catalyzed asymmetric hydrogenation of acylamides

图式10. Co/OIP催化1,1-二芳基烯烃的不对称氢化反应

Scheme 10. Co/OIP-catalyzed asymmetric hydrogenation of 1,1-diaromatic olefins

图式11. Co催化末端炔烃区域选择性与对映选择性的顺序氢硅化/氢化反应

Scheme 11. Co-catalyzed regio- and enantioselective sequential hydrosilylation/hydrogenation of terminal alkynes

图式12. 钴催化内炔不对称顺序氢硼化/氢化反应

Scheme 12. Co-catalyzed asymmetric sequential hydroboration/hydrogenation of internal alkynes

图式13. 钴催化烯酮与HBpin的不对称1,4-氢硼化反应

Scheme 13. Co-catalyzed asymmetric 1,4-hydroboration of enones with HBpin

图式14. 钴催化E/Z异构烯烃的对映体汇聚氢化反应

Scheme 14. Co-catalyzed enantiomeric convergent hydrogenation of E/Z-isomerized olefins

图式15. 钴催化乙烯基硅烷的不对称氢化反应

Scheme 15. Co-catalyzed asymmetric hydrogenation of vinyl silanes

图式16. 钴催化α,β-不饱和羧酸的不对称氢化反应

Scheme 16. Co-catalyzed asymmetric hydrogenation of α,β- unsaturated carboxylic acids

图式17. 钴催化四取代环状烯烃的不对称氢化反应

Scheme 17. Co-catalyzed asymmetric hydrogenation of tetra-substituted cycloalkenes

图式18. 钴催化共轭烯炔的化学选择性与对映选择性氢化反应

Scheme 18. Co-catalyzed chemo-/enantioselective hydrogenation of conjugated enynes

图式19. 钴催化的连续不对称氢化合成手性Z-烯丙酰胺

Scheme 19. Synthesis of chiral Z-allylamides by Co-catalyzed asymmetric sequential hydrogenations

图式20. 唑类基团导向的钴催化烯烃不对称氢化反应

Scheme 20. Azole-directed Co-catalyzed asymmetric hydrogenation of alkenes

图式21. 钴催化E/Z-烯酰胺对映体汇聚不对称氢化反应

Scheme 21. Co-catalyzed enantiomeric convergent asymmetric hydrogenation of E/Z-Enamides

图式22. 钴催化三取代环状烯酰胺的不对称氢化合成手性环状酰胺

Scheme 22. Co-catalyzed enantioselective hydrogenation of trisubstituted carbocyclic olefins to chiral cyclic amides

图式23. 钴催化对1-茚酮缩烯胺的不对称氢化反应及雷沙吉兰的合成

Scheme 23. Co-catalyzed asymmetric hydrogenation of 1-inda- none enamides and synthesis of Rasagiline

图式24. 钴催化α-酰胺基丙烯酸酯的不对称氢化和氘代氢化反应

Scheme 24. Co-catalyzed asymmetric hydrogenation and deuteriohydrogenation of α-amido acrylates

图式25. 镍催化烯烃不对称转移氢化合成手性α-氨基酸和β-氨基酸

Scheme 25. Synthesis of chiral α-amino acids and β-amino acids by nickel-catalyzed asymmetric transfer hydrogenation

图式26. 镍催化缺电子烯烃的不对称转移氢化反应

Scheme 26. Ni-catalyzed asymmetric transfer hydrogenation of electron-deficient olefins

图式27. DMF作氢源的镍催化α,β-不饱和酯的不对称转移氢化反应

Scheme 27. Ni-catalyzed asymmetric transfer hydrogenation of α,β-unsaturated esters with DMF as hydride source

图式28. 镍催化α,β-不饱和酯的不对称氢化反应

Scheme 28. Ni-catalyzed asymmetric hydrogenation of α,β- unsaturated esters

图式29. 镍催化官能团化烯酰胺和不饱和酯的不对称氢化反应

Scheme 29. Ni-catalyzed asymmetric hydrogenation of functionalized enamides and unsaturated esters

图式30. 镍催化γ,γ-二取代环己二烯酮的不对称氢化反应

Scheme 30. Ni-catalyzed desymmetric hydrogenation of γ,γ-di- substituted cyclohexadienones

图式31. 镍催化2-酰胺基丙烯酸酯不对称氢化反应

Scheme 31. Ni-catalyzed asymmetric hydrogenation of 2-amidoacrylates

图式32. 镍催化的不对称转移氢化α,β-不饱和酯、腈、酮及烯丙醇

Scheme 32. Ni-catalyzed asymmetric transfer hydrogenation of α,β-unsaturated esters, nitriles, ketones and allylic alcohols

图式33. 镍催化2-噁唑酮的不对称氢化反应

Scheme 33. Ni-catalyzed asymmetric hydrogenation of 2-oxa- zolones

图式34. 镍催化环状烯基砜苯并[b]噻吩1,1-二氧化物的不对称氢化反应

Scheme 34. Ni-catalyzed asymmetric hydrogenation of cyclic alkenyl sulfones benzo[b]thiophene 1,1-dioxides

图式35. 镍催化不饱和无环和环状β-氨基酸衍生物的不对称转移氢化反应

Scheme 35. Ni-catalyzed asymmetric transfer hydrogenation of unsaturated acyclic and cyclic β-amino acid derivatives

图式36. 镍催化β,β-二取代丙烯酸不对称氢化反应

Scheme 36. Ni-catalyzed asymmetric hydrogenation of β,β-disubstituted acrylic acids

图式37. 镍催化α,β-不饱和氨基酸衍生物的不对称氢化反应

Scheme 37. Ni-catalyzed asymmetric hydrogenation of α,β-unsaturated amino acid derivatives

图式38. 镍催化α-取代乙烯基膦酸酯和二芳基乙烯基膦氧化物的不对称氢化反应

Scheme 38. Ni-catalyzed asymmetric hydrogenation of α-substituted vinylphosphonates and diarylvinylphosphine oxides

图式39. 镍催化α-取代丙烯酸不对称转移氢化反应

Scheme 39. Ni-catalyzed transfer hydrogenation of α-substituted arcylic acids

图式40. 镍催化外消旋四取代烯丙基的高区域选择性和高对映选择性半氢化反应

Scheme 40. Ni-catalyzed highly regio- and enantioselective semi-hydrogenation of racemic tetrasubstituted allenes

图式41. 镍催化α-取代丙烯酸不对称氢化反应

Scheme 41. Ni-catalyzed hydrogenation of α-substituted arcylic acids

图式42. 镍催化不对称氢化合成手性β2-氨基磷衍生物

Scheme 42. Synthesis of chiral β2-amino phosphorus derivatives via Ni-catalyzed asymmetric hydrogenation

图式43. 镍催化α-亚烷基琥珀酰亚胺的不对称氢化反应

Scheme 43. Ni-catalyzed asymmetric hydrogenation of α-alkyli- denesuccinimides

图式44. 镍催化α-取代丙烯酸不对称转移氢化反应

Scheme 44. Ni-catalyzed transfer hydrogenation of α-substi- tuted arcylic acids

图式45. 镍催化三取代烯酮的不对称迭代1,2-氢化反应

Scheme 45. Ni-catalyzed asymmetric iterative 1,2-hydrogenation of trisubstituted enones

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