The new chiral ligands I-III based on derivatives of imidazolidin-4-one were synthesised and characterised. The catalytic activity and enantioselectivity of their corresponding copper(II) complexes were studied in asymmetric Henry reactions. It was found that the enantioselectivity of these catalysts is overall very high and depends on the relative configuration of the ligand used; cis-configuration of ligand affords the nitroaldols with major enantiomer S- (up to 97% ee), whereas the application of ligands with trans-configuration led to nitroaldols with major R-enantiomer (up to 96% ee). The "proline-type" ligand IV was also tested in asymmetric aldol reactions. Under the optimised reaction conditions, aldol products with enantioselectivities of up to 91% ee were obtained.

Institute of Organic Chemistry and Technology Faculty of Chemical Technology University of Pardubice Studentská 573 532 10 Pardubice Czech Republic

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Mikami K, Lautens M, editors. New Frontiers in Asymmetric Catalysis. New Jersey: John Wiley & Sons; 2007. DOI

Caprio V, Williams J M J. Catalysis in Asymmetric Synthesis. Oxford, UK: John Wiley & Sons; 2009.

Zhou Q-L, editor. Privileged Chiral Ligands and Catalysts. Weinheim, Germany: Wiley-VCH; 2011. DOI

Steinlandt P S, Zhang L, Meggers E. Chem Rev. 2023;123:4764–4794. doi: 10.1021/acs.chemrev.2c00724. PubMed DOI PMC

Panov I, Drabina P, Padělková Z, Šimůnek P, Sedlák M. J Org Chem. 2011;76:4787–4793. doi: 10.1021/jo200703j. PubMed DOI

Drabina P, Karel S, Panov I, Sedlák M. Tetrahedron: Asymmetry. 2013;24:334–339. doi: 10.1016/j.tetasy.2013.02.007. DOI

Drabina P, Horáková E, Růžičková Z, Sedlák M. Tetrahedron: Asymmetry. 2015;26:141–147. doi: 10.1016/j.tetasy.2015.01.001. DOI

Harmand L, Drabina P, Pejchal V, Husáková L, Sedlák M. Tetrahedron Lett. 2015;56:6240–6243. doi: 10.1016/j.tetlet.2015.09.112. DOI

Nováková G, Drabina P, Frumarová B, Sedlák M. Adv Synth Catal. 2016;358:2541–2552. doi: 10.1002/adsc.201600198. DOI

Bhosale D S, Drabina P, Kincl M, Vlček M, Sedlák M. Tetrahedron: Asymmetry. 2015;26:1300–1306. doi: 10.1016/j.tetasy.2015.10.003. DOI

Bhosale D S, Drabina P, Palarčík J, Hanusek J, Sedlák M. Tetrahedron: Asymmetry. 2014;25:334–339. doi: 10.1016/j.tetasy.2014.01.001. DOI

Panov I, Drabina P, Hanusek J, Sedlák M. Synlett. 2013;24:1280–1282. doi: 10.1055/s-0033-1338803. DOI

Drabina P, Feixová V, Sedlák M. Tetrahedron Lett. 2019;60:99–101. doi: 10.1016/j.tetlet.2018.11.067. DOI

Vrbický M, Macek K, Pochobradský J, Svoboda J, Sedlák M, Drabina P. Beilstein J Org Chem. 2022;18:438–445. doi: 10.3762/bjoc.18.46. PubMed DOI PMC

Desimoni G, Faita G, Quadrelli P. Chem Rev. 2003;103:3119–3154. doi: 10.1021/cr020004h. PubMed DOI

Arai T, Mishiro A, Yokoyama N, Suzuki K, Sato H. J Am Chem Soc. 2010;132(15):5338–5339. doi: 10.1021/ja100265j. PubMed DOI

Dalko P I, editor. Enantioselective Organocatalysis: Reaction and Experimental Procedures. Weinheim, Germany: Wiley-VCH; 2007. DOI

Hathaway B J. Copper. In: Wilkinson G, editor. Comprehensive Coordination Chemistry. 5, Chapter 53. New York: Pergamon Press; 1987. pp. 533–774.

Evans D A, Seidel D, Rueping M, Lam H W, Shaw J T, Downey C W. J Am Chem Soc. 2003;125:12692–12693. doi: 10.1021/ja0373871. PubMed DOI

Hartikka A, Arvidsson P I. Tetrahedron: Asymmetry. 2004;15:1831–1834. doi: 10.1016/j.tetasy.2004.04.029. DOI

Torii H, Nakadai M, Ishihara K, Saito S, Yamamoto H. Angew Chem, Int Ed. 2004;43:1983–1986. doi: 10.1002/anie.200352724. PubMed DOI

Grondal C, Enders D. Tetrahedron. 2006;62:329–337. doi: 10.1016/j.tet.2005.09.060. DOI

Thayumanavan R, Tanaka F, Barbas C F. Org Lett. 2004;6(20):3541–3544. doi: 10.1021/ol0485417. PubMed DOI

Zhang B, Jiang Z, Zhou X, Lu S, Li J, Liu Y, Li C. Angew Chem, Int Ed. 2012;51:13159–13162. doi: 10.1002/anie.201206438. PubMed DOI

Yamashita Y, Yasukawa T, Yoo W-J, Kitanosono T, Kobayashi S. Chem Soc Rev. 2018;47:4388–4480. doi: 10.1039/c7cs00824d. PubMed DOI