Abstract
Background: Multistranded foldamers mimic biopolymer architecture, through the assembly and folding of intrinsically flexible polymeric chains attached to polyol core have been synthesised here. The synthesised dendritic motifs possess helical cavities with properly arranged active sites. As these cavities are large enough to accommodate guest molecules, their application as synthetic foldamer catalyst were investigated in Knoevenagel and Mannich reactions.
Methods: It is presumed to be the potentiality of dendritic foldamers to form reverse micelle in the interior of helical motif containing many reactive sites.
Results: Inside the dendritic foldamer, the substrates are adequately concentrated, work together in cooperation for ligand-binding, and stabilize the transition state as in enzymes that helps to accelerate the reaction rate many times greater than in bulk solution.
Conclusion: An unrivalled reaction rate and high yield of products were obtained within a short time in both Knoevenagel and Mannich reactions by using dendritic foldamers as catalysts.
Keywords: Dendrimer, hyperbranched polymer, dendritic foldamer, nanosized cavities, reverse micelle, Organocatalysis, Knoevenagel condensation, Mannich reaction.
[http://dx.doi.org/10.1038/nature16511] [PMID: 26789245]
[http://dx.doi.org/10.1038/nature16496] [PMID: 26760202]
[http://dx.doi.org/10.1016/j.celrep.2016.01.025] [PMID: 26854230]
[http://dx.doi.org/10.1146/annurev.biophys.35.040405.102053] [PMID: 16689632]
[http://dx.doi.org/10.2174/1567205012666150504145646] [PMID: 25938871]
[http://dx.doi.org/10.1021/acs.chemrev.8b00038] [PMID: 30281290]
[http://dx.doi.org/10.1021/ja070396f] [PMID: 17362016]
[http://dx.doi.org/10.1021/acs.accounts.8b00048] [PMID: 29672021]
[http://dx.doi.org/10.1021/ar900036b] [PMID: 19813703]
[http://dx.doi.org/10.1073/pnas.1620179114] [PMID: 28831002]
[http://dx.doi.org/10.1007/s00726-011-0893-3] [PMID: 21455734]
[http://dx.doi.org/10.1039/b909034g] [PMID: 20449051]
[http://dx.doi.org/10.1021/ar5000242] [PMID: 24673152]
[http://dx.doi.org/10.1021/ja993830p]
[http://dx.doi.org/10.1126/science.1200143] [PMID: 21385710]
[http://dx.doi.org/10.1038/s41570-020-0180-5] [PMID: 37127955]
[http://dx.doi.org/10.1021/jacs.7b00181] [PMID: 28234005]
[http://dx.doi.org/10.1002/anie.200804996] [PMID: 19090515]
[http://dx.doi.org/10.1021/ja067670a] [PMID: 17419626]
[http://dx.doi.org/10.1073/pnas.0307443101] [PMID: 15054138]
[http://dx.doi.org/10.1021/cr5005315] [PMID: 25716119]
[http://dx.doi.org/10.1021/cr000045i] [PMID: 11710070]
[http://dx.doi.org/10.1021/cr900162q] [PMID: 19905011]
[http://dx.doi.org/10.1073/pnas.0903187106] [PMID: 19667204]
[http://dx.doi.org/10.1039/c1cc11137j] [PMID: 21483969]
[http://dx.doi.org/10.1021/acs.biomac.9b01090] [PMID: 31517479]
[http://dx.doi.org/10.1039/C5CC03016A] [PMID: 26073994]
[http://dx.doi.org/10.1038/nchem.2353] [PMID: 26492006]
[http://dx.doi.org/10.1021/ja063164+] [PMID: 16939241]
[http://dx.doi.org/10.1039/C4OB00447G] [PMID: 24756480]
[http://dx.doi.org/10.1021/acs.chemrev.6b00354] [PMID: 27754649]
[http://dx.doi.org/10.3390/nano10071403] [PMID: 32707641]
[http://dx.doi.org/10.1021/acsnano.7b02618] [PMID: 28590117]
[http://dx.doi.org/10.1021/es506351r] [PMID: 25837659]
[http://dx.doi.org/10.1002/chem.202001767] [PMID: 32428312]
[http://dx.doi.org/10.1016/j.polymer.2017.05.054]
[http://dx.doi.org/10.1016/j.tet.2019.130676]
[http://dx.doi.org/10.1002/slct.202000770]
[http://dx.doi.org/10.1021/acs.chemmater.8b03238]
[http://dx.doi.org/10.1002/asia.200700185] [PMID: 17763496]
[http://dx.doi.org/10.1021/ja068951l] [PMID: 17343383]
[http://dx.doi.org/10.1073/pnas.211536998] [PMID: 11593011]
[http://dx.doi.org/10.1007/b135681]
[http://dx.doi.org/10.1093/molbev/msr300] [PMID: 22144639]
[http://dx.doi.org/10.1128/AEM.01239-17] [PMID: 28710270]
[http://dx.doi.org/10.1073/pnas.162277099] [PMID: 12177422]
[http://dx.doi.org/10.1073/pnas.0508783103] [PMID: 16488977]
[http://dx.doi.org/10.1039/a903001h] [PMID: 11902439]
[http://dx.doi.org/10.1021/ar960298r]
[http://dx.doi.org/10.1021/acsomega.8b00681] [PMID: 31458731]
[http://dx.doi.org/10.1039/b801793j] [PMID: 19421588]
[http://dx.doi.org/10.1021/jacs.7b05802]
[http://dx.doi.org/10.1073/pnas.0913638107] [PMID: 20194782]
[http://dx.doi.org/10.1039/b921020b] [PMID: 20162147]
[http://dx.doi.org/10.1016/j.arabjc.2014.04.008]
[http://dx.doi.org/10.1016/j.fuproc.2016.03.016]
[http://dx.doi.org/10.1039/c2cs15305j] [PMID: 22310886]
[http://dx.doi.org/10.1016/j.chembiol.2008.09.015] [PMID: 19318207]
[http://dx.doi.org/10.1039/C3CS60037H] [PMID: 24365792]
[http://dx.doi.org/10.1038/s41467-018-06872-0] [PMID: 30356038]
[http://dx.doi.org/10.1021/ma00094a033]
[http://dx.doi.org/10.3998/ark.5550190.0007.f06]
[http://dx.doi.org/10.1002/ejoc.200600335]
[http://dx.doi.org/10.1002/app.41593]
[http://dx.doi.org/10.1002/aoc.2941]
[http://dx.doi.org/10.1039/b918595j]
[http://dx.doi.org/10.3998/ark.5550190.0012.b14]
[http://dx.doi.org/10.1021/ol991113u]
[http://dx.doi.org/10.3390/ijms15058656] [PMID: 24837832]
[http://dx.doi.org/10.1016/j.catcom.2010.02.007]
[http://dx.doi.org/10.1016/j.reactfunctpolym.2021.104827]
[http://dx.doi.org/10.1002/jhet.4361]