淀粉及其衍生物负载金属催化剂在有机反应中的应用研究进展

doi:10.6023/cjoc202601031

摘要/Abstract

淀粉作为储量丰富、可再生、可生物降解的天然多糖, 因其独特的螺旋结构、丰富的羟基官能团以及易于化学修饰的特性, 在构建绿色非均相金属催化剂方面展现出巨大潜力. 综述了2005~2025年间淀粉及其衍生物负载金属催化剂在有机反应中的应用进展. 依据淀粉载体的连接官能团或功能化方式, 将其归纳为羟基直接配位型、氨基/席夫碱功能化型、离子液体功能化型、磁性复合功能化型、天然小分子修饰型和有机-无机杂化型六大类, 并评述了其制备策略、金属固定方式、催化性能及循环稳定性. 淀粉负载金属催化剂已成功应用于C—C偶联反应、点击化学反应、多组分反应、氧化还原反应以及生物质转化等重要有机反应中, 表现出较高的催化活性、良好的底物适用范围和循环性能. 最后, 对该领域面临的挑战和发展方向进行了展望.

关键词: 淀粉负载金属催化剂, 有机反应, 非均相催化, 绿色化学

Starch, an abundant, renewable, and biodegradable natural polysaccharide, has shown great potential in constructing green heterogeneous metal catalysts due to its unique helical structure, abundant hydroxyl functional groups, and facile chemical modification. This review summarizes the research progress on starch and its derivatives supported metal catalysts in organic reactions from 2005 to 2025. According to the anchoring functional groups or functionalization modes of the starch supports, these catalytic systems are classified into six categories: direct hydroxyl-coordination, amino/Schiff base functionalized, ionic liquid functionalized, magnetic composite functionalized, natural small-molecule modified, and organic-inorganic hybrid systems. Their preparation strategies, metal immobilization modes, catalytic performance, and recycling stability are discussed. Starch-supported metal catalysts have been successfully applied to important organic transformations including C—C coupling reactions, click reactions, multicomponent reactions, oxidation and reduction reactions, and biomass conversion. These catalysts exhibit high catalytic activity, broad substrate scope, and good recyclability. Finally, the current challenges and future development prospects of starch-supported metal catalyst systems are discussed.

Key words: starch-supported metal catalysts, organic reactions, heterogeneous catalysis, green chemistry

引用此文

莫百川, 李婷婷, 王芳, 巴达日夫. 淀粉及其衍生物负载金属催化剂在有机反应中的应用研究进展[J]. 有机化学, 2026, 46(10): 3933-3962.

Baichuan Mo, Tingting Li, Fang Wang, Darifu Ba. Research Progress on Applications of Starch and Its Derivatives Supported Metal Catalysts in Organic Reactions[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 3933-3962.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 31

图1. 淀粉两种主要组分的化学结构: (a)直链淀粉和(b)支链淀粉

Figure 1. Chemical structure of two main components of starch: (a) amylose chain, and (b) amylopectin chain

图式1. 催化剂ECS-SB-CuBr的合成[25]

Scheme 1. Synthesis of ECS-SB-CuBr catalyst[25]

图式2. 催化剂Star-Cu(OAc)2的制备[26]

Scheme 2. Preparation of Star-Cu(OAc)2 catalyst[26]

图式3. AmP-SNC/Pd(0)催化剂的合成路线[28]

Scheme 3. Synthesis route of AmP-SNC/Pd(0) catalyst[28]

图式4. NH2-NCS@PdCl2催化剂的合成[29]

Scheme 4. Synthesis of NH2-NCS@PdCl2 catalyst[29]

图式5. 催化剂SNP-NH2/Pd(0)的合成路线[30]

Scheme 5. Synthesis route of SNP-NH2/Pd(0) catalyst[30]

图式6. 催化剂PEIS@Pd(0)的合成路线[31]

Scheme 6. Synthetic route of PEIS@Pd(0) catalyst[31]

图式7. 催化剂ST-Sc-Pd和ST-Shf-Pd的合成路线[32-33]

Scheme 7. Synthetic route of ST-Sc-Pd and ST-Shf-Pd catalysts[32-33]

图式8. Starch-SB-Pd(II)催化剂的制备示意图[34]

Scheme 8. Schematic diagram for the preparation of Starch-SB-Pd(II) catalyst[34]

图式9. 淀粉负载氧钒席夫碱催化剂的合成路线[35]

Scheme 9. Synthetic route to starch immobilized oxo-vanadium Schiff base catalyst[35]

图式10. ECS-MoO2(acac)2催化剂的制备[36]

Scheme 10. Preparation of ECS-MoO2(acac)2 catalyst[36]

图式11. ECS-Ni(acac)2催化剂的制备[38]

Scheme 11. Preparation of ECS-Ni(acac)2 catalyst[38]

图式12. Starch-Fe3O4@IL-TZ-Pd催化剂的合成路线[39]

Scheme 12. Synthetic route toward the Starch-Fe3O4@IL-TZ-Pd catalyst[39]

图式13. Fe-NHC/expanded HACS和Fe-NHC/S350催化剂的制备[40]

Scheme 13. Preparation of Fe-NHC/expanded HACS and Fe-NHC/S350 catalysts[40]

图式14. ECS-IL-RuCl3催化剂的合成[41]

Scheme 14. Synthesis of ECS-IL-RuCl3 catalyst[41]

图式15. ECS-IL-Al(NO3)3催化剂的合成[42]

Scheme 15. Synthesis of ECS-IL-Al(NO3)3 catalyst[42]

图式16. MNP@SPAAm/Cu催化剂的合成路线[43]

Scheme 16. Synthetic route of MNP@SPAAm/Cu catalyst[43]

图式17. CuFe2O4@Starch催化剂的制备[44]

Scheme 17. Preparation of CuFe2O4@Starch catalyst[44]

图式18. 催化剂Pd@Fe3O4-NH2/Starch的合成路线[48]

Scheme 18. Synthetic route of Pd@Fe3O4-NH2/Starch catalyst[48]

图式19. Pd(II)NA2@SMNP催化剂的合成[49]

Scheme 19. Synthesis of Pd(II)NA2@SMNP catalyst[49]

图式20. Fe3O4-starch/AgNPs催化剂的制备[54]

Scheme 20. Preparation of Fe3O4-starch/AgNPs catalyst[54]

图式21. 催化剂CoL2@SMNP的制备[55]

Scheme 21. Preparation of CoL2@SMNP catalyst[55]

图式22. MNP@Seed starch@FR-Co催化剂的制备[56]

Scheme 22. Preparation of MNP@Seed starch@FR-Co catalyst[56]

图式23. ZrOL2@SMNP催化剂的合成路线[60]

Scheme 23. Synthetic route of ZrOL2@SMNP catalyst[60]

图式24. Fe3O4@DAS@VB1@CuCl催化剂的制备[61]

Scheme 24. Preparation of Fe3O4@DAS@VB1@CuCl catalyst[61]

图式25. 催化剂Fe3O4@St-His/Cu的合成[62]

Scheme 25. Synthesis of Fe3O4@St-His/Cu catalyst[62]

图式26. 催化剂starch-crt@Au的合成[63]

Scheme 26. Synthesis of starch-crt@Au catalyst[63]

图式27. ASS-Cu(acac)2催化剂的制备[64]

Scheme 27. Preparation of ASS-Cu(acac)2 catalyst[64]

图式28. 催化剂PNP-SSS的合成路线[65]

Scheme 28. Synthetic route of PNP-SSS catalyst[65]

图式29. 催化剂Pd-MNPSS的合成路线[68]

Scheme 29. Synthetic route of Pd-MNPSS catalyst[68]

图式30. Pd@Hal-SA催化剂的制备[69]

Scheme 30. Preparation of Pd@Hal-SA catalyst[69]

参考文献 69

[1]	Nasrollahzadeh M.; Sajjadi M.; Iravani S.; Varma R. S. Carbohydr. Polym. 2021, 251, 116986. doi: 10.1016/j.carbpol.2020.116986
[2]	Nasrollahzadeh M.; Shafiei N.; Nezafat Z.; Bidgoli S. S. N.; Soleimani F. Carbohydr. Polym. 2020, 241, 116353. doi: 10.1016/j.carbpol.2020.116353
[3]	Dohendou M.; Pakzad K.; Nezafat Z.; Nasrollahzadeh M.; Dekamin M. G. Int. J. Biol. Macromol. 2021, 192, 771. doi: 10.1016/j.ijbiomac.2021.09.162
[4]	Zhao M.; Wu Y. X.; Cao J.-P. Appl. Organomet. Chem. 2020, 34, e5539.
[5]	Del Zotto A.; Zuccaccia D. Catal. Sci. Technol. 2017, 7, 3934. doi: 10.1039/C7CY01201B
[6]	Veisi H.; Neyestani N.; Pirhayati M.; Kamangar S. A.; Lotfi S.; Tamoradi T.; Karmakar B. RSC Adv. 2021, 11, 22278. doi: 10.1039/D1RA02634H
[7]	Rad M. N. S.; Behrouz S.; Doroodmand M. M.; Moghtaderi N. Synthesis 2011, 23, 3915.
[8]	Molnár Á.; Papp A. Catal. Sci. Technol. 2014, 4, 295. doi: 10.1039/C3CY00699A
[9]	Wolfson A.; Levy-Ontman O. Mol. Catal. 2020, 493, 111048.
[10]	Chtchigrovsky M.; Primo A.; Gonzalez P.; Molvinger K.; Robitzer M.; Quignard F.; Taran F. Angew. Chem., Int. Ed. 2009, 48, 5196.
[11]	Channab B.-E.; El Idrissi A.; Zahouily M.; Essamlali Y.; White J. C. Int. J. Biol. Macromol. 2023, 238, 124075. doi: 10.1016/j.ijbiomac.2023.124075
[12]	Tester R. F.; Karkalas J.; Qi X. J. Cereal Sci. 2004, 39, 151. doi: 10.1016/j.jcs.2003.12.001
[13]	Zarski A.; Bajer K.; Kapuśniak J. Polymers 2021, 13, 832. doi: 10.3390/polym13050832
[14]	Khlestkin V. K.; Peltek S. E.; Kolchanov N. A. Carbohydr. Polym. 2018, 181, 460. doi: 10.1016/j.carbpol.2017.10.035
[15]	Abd El-Ghany N. A.; Elella M. H. A.; Abdallah H. M.; Mostafa M. S.; Samy M. J. Polym. Environ. 2023, 31, 2792. doi: 10.1007/s10924-023-02798-x
[16]	Corre D. L.; Bras J.; Dufresne A. Biomacromolecules 2010, 11, 1139. doi: 10.1021/bm901428y
[17]	Dereje B. Int. J. Biol. Macromol. 2021, 187, 911. doi: 10.1016/j.ijbiomac.2021.07.188 pmid: 34358600
[18]	Gholinejad M.; Saadati F.; Shaybanizadeh S.; Pullithadathil B. RSC Adv. 2016, 6, 4983. doi: 10.1039/C5RA22292C
[19]	Saadati F.; Gholinejad M.; Janmohammadi H.; Shaybanizadeh S. Lett. Org. Chem. 2018, 15, 79.
[20]	Wongmanee K.; Khuanamkam S.; Chairam S. J. King Saud Univ., Sci. 2017, 29, 547. doi: 10.1016/j.jksus.2017.08.007
[21]	Chairam S.; Konkamdee W.; Parakhun R. J. Saudi Chem. Soc. 2017, 21, 656. doi: 10.1016/j.jscs.2015.11.001
[22]	Chong H.-B.; Gao G.-Q.; Li G. Chin. J. Chem. Phys. 2019, 32, 747. doi: 10.1063/1674-0068/cjcp1905101
[23]	Amininia A.; Pourshamsian K.; Sadeghi B. Russ. J. Org. Chem. 2020, 56, 1279. doi: 10.1134/S1070428020070234
[24]	Teli P.; Teli S.; Sahiba N.; Soni S.; Agarwal S. Appl. Organomet. Chem. 2024, 38, e7393.
[25]	Hong M.; Min J.; Wu S. Y.; Li J. T.; Wang J.; Wei L. F.; Ling Z.; Li K.; Wang S. F. Appl. Organomet. Chem. 2020, 34, e5411.
[26]	Gupta P.; Kumar P.; Syal B.; Shamim T. Res. Chem. Intermed. 2022, 48, 4601. doi: 10.1007/s11164-022-04829-z
[27]	Gronnow M. J.; Luque R.; Macquarrie D. J.; Clark J. H. Green Chem. 2005, 7, 552. doi: 10.1039/b501130b
[28]	Verma S.; Tripathi D.; Gupta P.; Singh R.; Bahuguna G. M.; Shivakumar K. L. N.; Chauhan R. K.; Saran S.; Jain S. L. Dalton Trans. 2013, 42, 11522. doi: 10.1039/c3dt51059j
[29]	Verma S.; Bras J. L.; Jain S. L.; Muzart J. Dalton Trans. 2013, 42, 14454. doi: 10.1039/c3dt51685g
[30]	Kumar S.; Verma S.; Jain S. L. Tetrahedron Lett. 2015, 56, 2430. doi: 10.1016/j.tetlet.2015.03.077
[31]	Fu L. X.; Deng W. X.; Liu L. J.; Peng Y. Q. Appl. Organomet. Chem. 2017, 31, e3853.
[32]	Baran T. J. Colloid Interface Sci. 2017, 496, 446. doi: 10.1016/j.jcis.2017.02.047
[33]	Baran T.; Baran N. Y.; Menteş A. Appl. Organomet. Chem. 2018, 32, e4076.
[34]	Li X. J.; Zhou Z. Q.; Wang Y. N.; Dong J. X.; Jia X. B.; Hu Z. G.; Wei Q. C.; Zhang W. W.; Jiang Y. Q.; Zhang J. J.; Dong Y. H. Int. J. Biol. Macromol. 2023, 233, 123596. doi: 10.1016/j.ijbiomac.2023.123596
[35]	Verma S.; Bras J. L.; Jain S. L.; Muzart J. Appl. Catal. A-Gen. 2013, 468, 334. doi: 10.1016/j.apcata.2013.08.007
[36]	Hong M.; Yao M.-Y.; Pan H. RSC Adv. 2015, 5, 91558. doi: 10.1039/C5RA14581C
[37]	Hong M.; Yan J.-M. Phosphorus, Sulfur Silicon Relat. Elem. 2017, 192, 985. doi: 10.1080/10426507.2017.1322084
[38]	Kumar S.; Jain S. L.; Sain B. Catal. Today 2012, 198, 204. doi: 10.1016/j.cattod.2012.05.028
[39]	Gholinejad M.; Mirmohammadi S.; Sansano J. M. ChemistrySelect 2021, 6, 13906. doi: 10.1002/slct.202103589
[40]	Matharu A. S.; Ahmed S.; Almonthery B.; Macquarrie D. J.; Lee Y.-S.; Kim Y. ChemSusChem 2018, 11, 716. doi: 10.1002/cssc.201702207 pmid: 29281175
[41]	Verma S.; Jain S. L.; Sain B. ChemCatChem 2011, 3, 1329. doi: 10.1002/cctc.v3.8
[42]	Hong M.; Wu S. Y.; Li J. T.; Wang J.; Wei L. F.; Li K. Catal. Commun. 2020, 136, 105909. doi: 10.1016/j.catcom.2019.105909
[43]	Pourjavadi A.; Motamedi A.; Hosseini S. H.; Nazari M. RSC Adv. 2016, 6, 19128. doi: 10.1039/C5RA25519H
[44]	Bonyasi R.; Gholinejad M.; Saadati F.; Nájera C. New J. Chem. 2018, 42, 3078. doi: 10.1039/C7NJ03284F
[45]	Kamalzare M.; Bayat M.; Maleki A. R. Soc. Open Sci. 2020, 7, 200385. doi: 10.1098/rsos.200385
[46]	Nasiri A.; Khalilzadeh M. A.; Zareyee D. Inorg. Nano-Met. Chem. 2023, 53, 1007.
[47]	Tajbakhsh M.; Mazhari M.; Mavvaji M. Org. Prep. Proced. Int. 2023, 55, 251. doi: 10.1080/00304948.2022.2134697
[48]	Sharma H.; Bhardwaj M.; Kour M.; Paul S. Mol. Catal. 2017, 435, 58.
[49]	Rezapour E.; Jafarpour M.; Rezaeifard A. Catal. Lett. 2018, 148, 3165. doi: 10.1007/s10562-018-2513-2
[50]	Patra D.; Panja S.; Saha A. Eur. J. Org. Chem. 2020, 2020, 878. doi: 10.1002/ejoc.v2020.7
[51]	Mohammadzadeh A.; Marjani A. P.; Zamani A. S. Afr. J. Chem. 2020, 73, 55.
[52]	Nasiri A.; Khalilzadeh M. A.; Zareyee D. J. Coord. Chem. 2022, 75, 256. doi: 10.1080/00958972.2022.2038369
[53]	Poshtmakhi S. A.; Rad-Moghadam K.; Hosseinzadeh H.; Toorchi-Roudsari S. ChemistrySelect 2023, 8, e202300533.
[54]	Lu J. W.; Zhang M. L.; El-kott A. F.; AlShehri M. A.; Negm S.; AlSheri A. S. J. Organomet. Chem. 2025, 1029, 123544. doi: 10.1016/j.jorganchem.2025.123544
[55]	Jafarpour M.; Rezaeifard A.; Yasinzadeh V.; Kargar H. RSC Adv. 2015, 5, 38460. doi: 10.1039/C5RA04718H
[56]	Arghan M.; Koukabi N.; Kolvari E. Appl. Organomet. Chem. 2019, 33, e5075.
[57]	Razikazemi S.; Rad-Moghadam K.; Toorchi-Roudsari S. New J. Chem. 2018, 42, 12476. doi: 10.1039/C8NJ00718G
[58]	Dharmendra D.; Chundawat P.; Vyas Y.; Ameta C. J. Chem. Sci. 2022, 134, 47. doi: 10.1007/s12039-022-02040-6
[59]	Marandi A.; Nasiri E.; Koukabi N.; Seidi F. Int. J. Biol. Macromol. 2021, 190, 61. doi: 10.1016/j.ijbiomac.2021.08.085
[60]	Jafarpour M.; Rezaeifard A. Transition Met. Chem. 2016, 41, 205. doi: 10.1007/s11243-015-0012-5
[61]	Rafiee F.; Abbaspour M.; Ziarani G. M. React. Funct. Polym. 2022, 170, 105106. doi: 10.1016/j.reactfunctpolym.2021.105106
[62]	Rezaee M.; Rafiee F.; Fardi E. Polyhedron 2024, 249, 116790. doi: 10.1016/j.poly.2023.116790
[63]	Gholinejad M.; Dasvarz N.; Shojafar M.; Sansano J. M. Inorg. Chim. Acta 2019, 495, 118965. doi: 10.1016/j.ica.2019.118965
[64]	Sodhi R. K.; Changotra A.; Paul S. Catal. Lett. 2014, 144, 1819. doi: 10.1007/s10562-014-1345-y
[65]	Khalafi-Nezhad A.; Panah F. Green Chem. 2011, 13, 2408. doi: 10.1039/c1gc15360a
[66]	Khalafi-Nezhad A.; Panah F. J. Organomet. Chem. 2012, 717, 141. doi: 10.1016/j.jorganchem.2012.07.039
[67]	Panahi F.; Daneshgar F.; Haghighi F.; Khalafi-Nezhad A. J. Organomet. Chem. 2017, 851, 210. doi: 10.1016/j.jorganchem.2017.09.037
[68]	Tukhani M.; Panahi F.; Khalafi-Nezhad A. ACS Sustainable Chem. Eng. 2018, 6, 1456. doi: 10.1021/acssuschemeng.7b03923
[69]	Sadjadi S.; Malmir M.; Heravi M. M.; Kahangi F. G. Int. J. Biol. Macromol. 2018, 118, 1903. doi: S0141-8130(18)33041-1 pmid: 30009905