| 168 | 0 | 52 |
| 下载次数 | 被引频次 | 阅读次数 |
手性多孔有机聚合物(CPOPs)是手性有机单元通过共价键连接形成的具有手性微环境的聚合物,不仅可以直接作为手性催化剂,还可以作为载体用于制备非均相的催化剂,因而具有广泛的应用前景。按照反应类型进行分类,综述了近些年不对称催化反应中手性多孔有机聚合物的研究进展,重点探讨了手性多孔有机聚合物的设计、制备、结构和应用,并对该领域存在的问题以及发展趋势进行了分析和展望。
Abstract:Chiral porous organic polymers(CPOPs) are polymers with chiral microenvironments formed by linking chiral organic units through covalent bonds. They can not only serve directly as chiral catalysts,but also act as supports for the preparation of heterogeneous catalysts,thus exhibiting broad application prospects. Herein,the recent advances in CPOPs of the asymmetric catalysis are summarized according to the reaction types,with a focus on their design,preparation,structure,and applications. The existing problems and development trends in this field are also analyzed and discussed.
[1]Sun J S,Zhao K,Wang H L,et al. Heterogeneous bisphosphine ligand-encapsulated Rh catalysts for heterogeneous hydroformylation of alkenes with CO2[J]. ACS Sustainable Chem Eng,2024,12(34):12736-12743.
[2]Wang H,Sun J Y,Cai X,et al. Porous organic polymers supported heterogeneous catalysts for hydroformylation reactions[J]. Eur J Inorg Chem,2024,27(23):1-12.
[3]Chen W M,Cai P Y,Zhou H C,et al. Bridging homogeneous and heterogeneous catalysis:phosphine-functionalized metal-organic frameworks[J]. Angew Chem Int Ed,2024,63(12):1-14.
[4]Sun M Y,Cheung S C,Wang X Z,et al. Structural reassignment of covalent organic framework-supported palladium species:heterogenized palladacycles as efficient catalysts for sustainable C-H activation[J]. ACS Cent Sci,2024,10(10):1848-1860.
[5]Alsudairy Z,Brown N,Campbell A,et al. Covalent organic frameworks in heterogeneous catalysis:recent advances and future perspective[J]. Mater Chem Front,2023,7(16):3298-3331.
[6]Han W K,Liu Y,Yan X D,et al. Coordination directed metal covalent organic frameworks[J]. Mater Chem Front,2023,7(15):2995-3010.
[7]Hao Q,Tao Y,Ding X S,et al. Porous organic polymers:a progress report in China[J]. Sci China Chem,2023,66(3):620-682.
[8]Song W L,Zhang Y,Trand C H,et al. Porous organic polymers with defined morphologies:Synthesis,assembly,and emerging applications[J]. Prog Polym Sci,2023,142:101691-101759.
[9]Ovian J M,VojáčkováP,Jacobsen E N,et al. Enantioselective transition-metal catalysis via an anionbinding approach[J]. Nature,2023,616(7955):84-89.
[10]Fan Q H,Ren C Y,Yeuang C H,et al. Highly effective soluble polymer-supported catalysts for asymmetric hydrogenation[J]. J Am Chem Soc,1999,121(32):7407-7408.
[11]Wang Z J,Deng G J,Li Y,et al. Enantioselective hydrogenation of quinolines catalyzed by Ir(BINAP)-cored dendrimers:dramatic enhancement of catalytic activity[J]. Org Lett,2007,9(7):1243-1246.
[12]Sun Q,Meng X J,Liu X,et al. Mesoporous cross-linked polymer copolymerized with chiral BINAP ligand coordinated to a ruthenium species as an efficient heterogeneous catalyst for asymmetric hydrogenation[J].Chem Commun,2012,48(85):10505-10507.
[13]Wang X,Li J,Lu S M,et al. Efficient enantioselective hydrogenation of quinolines catalyzed by conjugated microporous polymers with embedded chiral BINAP ligand[J]. Chin J Catal,2015,36(8):1170-1174.
[14]Wang T,Lyu Y,Chen X K,et al. Ru coordinated with BINAP in knitting aryl network polymers for heterogeneous asymmetric hydrogenation of methyl acetoacetate[J]. RSC Adv,2016,6(34):28447-28450.
[15]Wang T,Lyu Y,Xiong K,et al. Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis[J]. Chin J Catal,2017,38(5):890-898.
[16]Sun Q,Dai Z F,Meng X J,et al. Homochiral porous framework as a platform for durability enhancement of molecular catalysts[J]. Chem Mater,2017,29(13):5720-5726.
[17]Nepal P,Kalapugama S,Shevlin M,et al. Polycationic Rh-josiphos polymers supported on phosphotungstic acid/Al2O3by multiple electrostatic attractions[J]. ACS Catal,2022,12(3):2034-2044.
[18]Zheng Z H,Yuan C,Sun M,et al. Construction of monophosphine-metal complexes in privileged diphosphine-based covalent organic frameworks for catalytic asymmetric hydrogenation[J]. J Am Chem Soc 2023,145(11):6100-6111.
[19]Wang C,Liao J Y,Xu A,et al. A highly efficient immobilization strategy for chiral ferrocene P,P-ligands with enhanced performance in asymmetric catalysis[J]. J Catal,2025,446:116080-116089.
[20]Tsubogo T,Yamashita Y,Kobayashi S,et al. Toward efficient asymmetric carbon-carbon bond formation:continuous flow with chiral heterogeneous catalysts[J]. Chem Eur J,2012,18(43):13624-13628.
[21]An W K,Han M Y,Wang C A,et al. Insights into the asymmetric heterogeneous catalysis in porous organic polymers:constructing a TADDOL-embedded chiral catalyst for studying the structure-activity relationship[J]. Chem Eur J,2014,20(35):11019-11028.
[22]Bissessar D,Achard T,Bellemin-Laponnaz S. Robust and recyclable self-supported chiral nickel catalyst for the enantioselective Michael addition[J]. Adv Synth Catal,2016,358(12):1982-1988.
[23]Wang J C,Kan X,Shang J Y,et al. Catalytic asymmetric synthesis of chiral covalent organic frameworks from prochiral monomers for heterogeneous asymmetric catalysis[J]. J Am Chem Soc,2020,142(40):16915-16920.
[24]Xu L,Cui J,Gao S,et al. Synthesis of Pd-stabilized chiral conjugated microporous polymer composites as high efficiency heterogeneous asymmetric Henry reaction catalysts[J]. Micro Mes Mater, 2022, 341:112075-112085.
[25]Li Y,Wang J M,Kan J L,et al. Combination of a metal-N-heterocyclic-carbene catalyst and a chiral aminocatalyst within a covalent organic framework:a powerful cooperative approach for relay asymmetric catalysis[J]. Inorg Chem,2022,61(5):2455-2462.
[26]Li F,Kan J L,Yao B J,et al. Synthesis of chiral covalent organic frameworks via asymmetric organocatalysis for heterogeneous asymmetric catalysis[J]. Angew Chem Int Ed,2022,61(25):1-7.
[27]Wang K X,Hou B,Dong J Q,et al. Controlling the degree of interpenetration in chiral three-dimensional covalent organic frameworks via steric tuning[J]. J Am Chem Soc,2024,146(31):21466-21475.
[28]Yu J T,Yang G,Gao M L,et al. Chiral ligand-decorated rhodium nanoparticles incorporated in covalent organic framework for asymmetric catalysis[J]. Angew Chem Int Ed,2024,63(46):1-6.
[29]Kang X,Wu X W,Han X,et al. Rational synthesis of interpenetrated 3D covalent organic frameworks for asymmetric photocatalysis[J]. Chem Sci,2020,11(6):1494-1502.
[30]Luo Y,Xu Z Y,Wang H,et al. Porous Ru(bpy)32+-linked polymers for recyclable photocatalysis of enantioselective alkylation of aldehydes[J]. ACS Macro Lett,2020,9(1):90-95.
[31]Li C Z,Ma Y H,Liu H R,et al. Asymmetric photocatalysis over robust covalent organic frameworks with tetrahydroquinoline linkage[J]. Chin J Catal,2020,41(8):1288-1297.
[32]Ma H C,Sun Y N,Chen G J,et al. A BINOL-phosphoric acid and metalloporphyrin derived chiral covalent organic framework for enantioselective a-benzylation of aldehydes[J]. Chem Sci,2022,13(7):1906-1911.
[33]Mishra K C,Dylana G Y,San M J,et al. Chiral perovskite nanocrystals for asymmetric reactions:a highly enantioselective strategy for photocatalytic synthesis of N-C axially chiral heterocycles[J]. J Am Chem Soc2023,145(31):17242-17252.
[34]Corkum E G,Hass M J,Sullivan A D,et al. A highly reusable rhodium catalyst-organic framework for the intramolecular cycloisomerization of 1,6-enynes[J]. Org Lett,2011,13(13):3522-3525.
[35]Wang B Y,Lin J,Sun Q S,et al. Efficient aliphatic C-H oxidation and C=C epoxidation catalyzed by porous organic polymer-supported single-site manganese catalysts[J]. ACS Catal,2021,11(17):10964-10973.
[36]Yin Z Y,He C C,Zhou Y,et al. Direct covalent immobilizaion of chiral phosphines to hollow mesoporous polystyrene nanospheres(HMPNs)for efficient heterogeneous enantioselective[2+3]cycloaddition[J]. App Catal A,2023,666:119413-119422.
[37]Zhang H,Xu B,Zhou L J,et al. Polymer-supported chiral palladium-based complexes as efficient heterogeneous catalysts for asymmetric reductive Heck reaction[J]. Green Syn Catal,2024,5(2):102-107.
[38]Bennedsen N R,Kramer S,Kegnæs S,et al. A chiral porous organic polymer as a heterogeneous ligand for enantioselective Pd-catalyzed C(sp3)-H functionalization[J]. Catal Sci Technol,2020,10(22):7697-7705.
基本信息:
DOI:10.16389/j.cnki.cn42-1737/n.2026.04.004
中图分类号:O621.251
引用信息:
[1]罗城,袁晨阳,张锦,等.手性多孔有机聚合物及其不对称催化反应研究进展[J].江汉大学学报(自然科学版),2026,54(04):37-48.DOI:10.16389/j.cnki.cn42-1737/n.2026.04.004.
基金信息:
江汉大学学生科研项目(2025yb107);江汉大学研究生科研创新基金项目(KYCXJJ202419)
2025-12-23
2025-12-23
2025-12-23