超分子催化旨在模拟天然酶的高效与特异性,配位分子笼因其可编程的纳米空腔而成为这一领域最有活力和发展前途的方向之一。硫代杯[4]芳烃及其氧化衍生物磺酰基杯[4]芳烃作为一类具有独特锥形构象和多配位点的“预组织”大环配体,能够与过渡金属离子组装形成结构明确、稳定性优异的多核簇次级构筑单元。基于“硫代/磺酰基杯[4]芳烃-金属簇”结构基元,结合不同的多羧酸桥联配体,已成功构筑了一系列拓扑丰富、尺寸可调的配位分子笼。借助于该类配位超分子体系,发展出多种催化功能化策略,包括利用空腔限域效应、在骨架上引入活性位点以及封装金属纳米颗粒等,成功实现了从简单模型反应到不对称合成、光/电催化、及串联反应等复杂化学转化。本综述系统总结了基于硫代/磺酰基杯[4]芳烃的配位分子笼在催化领域的最新研究进展,着重分析了该领域从“依赖空腔物理限域”向“理性设计协同催化”的范式演进过程,并特别强调了赋予催化选择性和效率的设计思路与设计原理,并为该领域未来的发展方向提供了展望。
Supramolecular catalysis aims to mimic the high efficiency and specificity of natural enzymes, and coordination cages have emerged as one of the most active and promising directions in this field due to their tunable nano-cavities. Thiacalix[4]arenes and their oxidized derivatives, sulfonylcalix[4]arenes, are a class of "preorganized" macrocyclic ligands with a unique cone conformation and multiple coordination sites. They can assemble with transition metal ions to form well-defined, highly stable polynuclear cluster secondary building units (SBUs). Based on this "thia-/sulfonyl-calix[4]arene-metal cluster" motif and employing various polycarboxylate bridging linkers, various coordination cages with diverse topologies and tunable dimensions have been successfully constructed. By virtue of this type of coordination supramolecular cages, researchers have developed several catalytic functionalization strategies, including exploiting the cavity confinement effect, introducing active sites into the cage backbone, and encapsulating catalytic guest species. These strategies have enabled a wide range of complex chemical transformations, from simple model reactions to asymmetric synthesis, photo/electrocatalysis, and cascade reactions. This review systematically summarizes the latest research progress on thia-/sulfonyl-calix[4]arene-based coordination cages in catalysis. It specifically analyzes the paradigm shift in this field from "relying on mere physical confinement" toward "rationally designed cooperative catalysis," with a particular emphasis on the design principles underlying enhanced catalytic selectivity and efficiency. Finally, the review provides perspectives on future directions for this field.
[1] Ringe D.; Petsko G.A.Science 2008, 320, 1428-1429.
[2] Warshel A.; Sharma P.K.; Kato M.; Xiang Y.; Liu H.; Olsson M.H.M.Chem. Rev. 2006, 106, 3210-3235.
[3] Hooley R.J.Nat. Chem. 2016, 8, 202-204.
[4] Meeuwissen J.; Reek J.N.Nat. Chem. 2010, 2, 615-621.
[5] Raynal M.; Ballester P.; Vidal-Ferran, A.; van Leeuwen, P.W.N.M.Chem. Soc. Rev. 2014, 43, 1734-1787.
[6] Wei H.; Wang E.Chem. Soc. Rev. 2013, 42, 6060-6093.
[7] Kremer C.; Lutzen A.Chem. Eur. J. 2013, 19, 6162-6196.
[8] Marchetti L.; Levine M.ACS Catal. 2011, 1, 1090-1118.
[9] Houk K.N.; Leach A.G.; Kim S.P.; Zhang X.Y.Angew. Chem. Int. Ed. 2003, 42, 4872-4897.
[10] Ward M.D.Chem. Commun. 2009, 4487-4499.
[11] Dalgarno S.J.; Power N.P.; Atwood J.L.Coord. Chem. Rev. 2008, 252, 825-841.
[12] Leininger S.; Olenyuk B.; Stang P.J.Chem. Rev. 2000, 100, 853-907.
[13] Zhou Y.; Yang J.; Jie K.Coord. Chem. Rev. 2025, 539, 216726.
[14] Amouri H.; Desmarets C.; Moussa J.Chem. Rev. 2012, 112, 2015-2041.
[15] Smulders M.M.J.; Riddell, I.A.; Browne, C.; Nitschke, J.R.Chem. Soc. Rev. 2013, 42, 1728-1754.
[16] Chakrabarty R.; Mukherjee P.S.; Stang P.J.Chem. Rev. 2011, 111, 6810-6918.
[17] Xie H.; Song M.; Fan Y.; Wang H.; Tu B.Chin. J. Chem . 2025, 43, 2613-2622.
[18] Gao W.-X.; Zhang H.-N.; Jin G.-X.Coord. Chem. Rev. 2019, 386, 69-84.
[19] Tan C.; Chu D.; Tang X.; Liu Y.; Xuan W.; Cui Y.Chem. Eur. J. 2019, 25, 662-672.
[20] Huang S.L.; Lin Y.J.; Hor T.S.A.; Jin, G.X.J. Am. Chem. Soc. 2013, 135, 8125-8128.
[21] Cullen W.; Misuraca M.C.; Hunter C.A.; Williams N.H.; Ward M.D.Nat. Chem. 2016, 8, 231-236.
[22] Ward M.D.; Hunter C.A.; Williams N.H.Acc. Chem. Res. 2018, 51, 2073-2082.
[23] Mu Q.S.; Wang X.Y.; Gao X.; Jin G.X.Chin. J. Chem . 2024, 43, 607-612.
[24] Yan B.; Song J.H.; Zhang D.L.; Guan Z.J.; Fang Y.Chin. J. Chem . 2025, 43, 1078-1089.
[25] Wang M.; Chen B.; Chen Q.; Wang J.; Chen M.; Jiang Z.; Wang P.Acta Chim. Sinica 2024, 82, 336.
[26] Morohashi N.; Narumi F.; Iki N.; Hattori T.; Miyano S.Chem. Rev. 2006, 106, 5291-5316.
[27] Kajiwara T.; Kobashi T.; Shinagawa R.; Ito T.; Takaishi S.; Yamashita M.; Iki N.Eur. J. Inorg. Chem. 2006, 2006, 1765-1770.
[28] Fan Y.-W.; Shi M.-X.; Wang Z.; Dai F.-R.; Chen Z.-N.Molecules 2024, 29, 1220.
[29] He C.; Sheng T.-P.; Dai F.-R.; Chen Z.-N.Chinese J. Struct. Chem. 2020, 39, 2077-2084
[30] Xue Y.; Hang X.; Ding J.; Li B.; Zhu R.; Pang H.; Xu Q.Coord. Chem. Rev. 2020, 430, 213656.
[31] Koblenz T.S.; Wassenaar J.; Reek J.N.H.Chem. Soc. Rev. 2008, 37, 247-262.
[32] Fang Y.; Powell J.A.; Li E.; Wang Q.; Perry Z.; Kirchon A.; Yang X.; Xiao Z.; Zhu C.; Zhang L.; Huang F.; Zhou, H.-C.Chem. Soc. Rev. 2019, 48, 4707-4730.
[33] Li C.C.; Cheng P.M.; Sun Q.F.Coord. Chem. Rev. 2026, 559.
[34] Pan M.; Yan X.H.; Jiao Z.W.; Wu K.; Xu H.S.; Xiao H.; Chen T.; Su C.Y.J. Chem. Educ. 2026, 103, 3835-3841.
[35] Qiao Y.; Zhang L.; Li J.; Lin W.; Wang Z.Angew. Chem. Int. Ed. 2016, 55, 12778-12782.
[36] Dai F.-R.; Qiao Y.; Wang Z.Inorg. Chem. Front. 2016, 3, 243-249.
[37] Bhuvaneswari N.; Annamalai K.P.; Dai F.-R.; Chen Z.-N.J. Mater. Chem. A 2017, 5, 23559-23565.
[38] Sheng T.-P.; Wei Y.; Jampani P.; Li C.; Dai F.-R.; Huang S.; Wang Z.; Chen Z.-N.Sci. China Chem. 2023, 66, 1714-1721.
[39] Li Q.; Zou Y.; Mao D.; Tian H.; Hang X.; Bi Y.Chem. Commun. 2025, 61, 9266-9269.
[40] Li C.; Sheng T.-P.; Wang Z.; Dai F.-R.Sci. China Chem. 2026, 69, 1840-1845.
[41] Lu Y.L.; Wang Y.P.; Wu K.; Pan M.; Su C.Y.Acc. Chem. Res. 2024, 57, 3277-3291.
[42] Ruan J.; Chen W.J.; Li Z.Q.; Hu P.; Su C.Y.Chin. J. Catal. 2026, 85, 346-355.
[43] Sheng T.-P.; He C.; Wang Z.; Zheng G.-Z.; Dai F.-R.; Chen Z.-N.CCS Chem. 2022, 4, 1098-1107.
[44] Tan C.; Jiao J.; Li Z.; Liu Y.; Han X.; Cui Y.Angew. Chem. Int. Ed. 2018, 57, 2085-2090.
[45] Tong H.Y.; Liang J.; Wu Q.J.; Zou Y.H.; Huang Y.B.; Cao R.Chem. Commun. 2021, 57, 2140-2143.
[46] Jin Y.; Jiang H.; Tang X.; Zhang W.; Liu Y.; Cui Y.Dalton Trans. 2021, 50, 8533-8539.
[47] Peng Y.; Mo Y.; Xie G.; Liang Y.; Chen J.; Fang Y.Small Structures 2026, 7, e202500901.
[48] Cai L.X.; Hu Y.H.; Zhou L.P.; Cheng P.M.; Guo X.Q.; Chan Y.T.; Sun Q.F.Chem. Sci. 2025, 16, 7956-7962.
[49] Zhong Y.-M.; Xuan J.-J.; Qin X.; Xiao H.; Xia Z.-J.; Zhou L.-P.; Guo X.-Q.; Hu Y.-H.; Zhang L.; Li C.; Cai L.-X.; Sun Q.-F.Sci. China Chem. 2024, 68, 561-569.
[50] Wang S.; Gao X.; Hang X.; Zhu X.; Han H.; Liao W.; Chen W.J. Am. Chem. Soc. 2016, 138, 16236-16239.
[51] Fang Y.; Li J.; Togo T.; Jin F.; Xiao Z.; Liu L.; Drake H.; Lian X.; Zhou H.-C.Chem 2018, 4, 555-563.
[52] Fang Y.; Xiao Z.; Li J.; Lollar C.; Liu L.; Lian X.; Yuan S.; Banerjee S.; Zhang P.; Zhou H.-C.Angew. Chem. Int. Ed. 2018, 57, 5283-5287.
[53] Fang Y.; Xiao Z.; Kirchon A.; Li J.; Jin F.; Togo T.; Zhang L.; Zhu C.; Zhou H.C. Chem. Sci.2019, 10, 3529-3534.
