Chiral Diazadioxocalix[2]arene[2]triazine-Based Derivative as Organocatalyst for Enantioselective Michael Reaction of Nitrostyrenes with Anthrone
Öz
Asymmetric synthesis, also known as chiral, enantioselective or stereoselective synthesis, is an organic synthesis which allows the formation of chiral compounds containing one or more stereogenic centers. Since different enantiomers of a molecule usually show different biological activity from each other, asymmetric synthesis is a very important topic in the pharmaceutical industry and organic chemistry. One of the most preferred methods to obtain a chiral compound from non-chiral compounds is the use of chiral catalysts. In this study, a chiral catalyst, which is not available in the literature, was synthesized for use in the asymmetric Michael reaction using anthrone and different nitrostyrene derivatives. First, diazadioxocalix[2]arene[2]triazine, which is available in the literature, was synthesized as the starting material of the chiral catalyst. (S)-(+)-1-cyclohexylethylamine was reacted with the synthesized starting material to obtain the substance to be used as a chiral catalyst in the enantioselective reaction. During the study, all reactions were monitored by thin layer chromatography and the obtained substances were purified by column chromatography. The structures of the purified products were elucidated by FTIR, 1H NMR and 13C NMR techniques and optical rotation angles were measured. The synthesized catalyst was tested in asymmetric Michael reaction and high yields and high enantioselectivity were obtained (95% yield and 98% ee).
Anahtar Kelimeler
Kaynakça
- M.W. Ha, S.M. Paek, Recent advances in the synthesis of ibuprofen and naproxen, Molecules. 26 (2021), 4792-4814. doi:10.3390/molecules26164792
- L. Albrecht, H. Jiang, K.A. Jørgensen, Hydrogen-bonding in aminocatalysis: From proline and beyond, Chemistry–A European Journal. 20 (2014), 358-368. doi:10.1002/chem.201303982
- B.T. Kumpuga, S. Itsuno, Synthesis of chiral polyesters of cinchona alkaloid catalysts for enantioselective Michael addition of anthrone to nitroalkenes, Journal of Catalysis. 361 (2018), 398–406. doi:10.1016/j.jcat.2018.03.020
- B. Kasprzyk-Hordern, Pharmacologically active compounds in the environment and their chirality, Chemical Society Reviews. 39 (2010), 4466-4503. doi:10.1039/C000408C
- M. Tsakos, C.G. Kokotos, Primary and secondary amine-(thio)ureas and squaramides and their applications in asymmetric organocatalysis, Tetrahedron. 69 (2013), 10199-10222. doi:10.1016/j.tet.2013.09.080
- Y. Wang, X. Xu, G. Wu, B. Pang, S. Liao, Y. Ji, Ligand-enabled C–H olefination and lactonization of benzoic acids and phenylacetic acids via palladium catalyst, Organic Letters. 24(3) (2022), 821-825. doi:10.1021/acs.orglett.1c04000
- Q. Zhang, B.F. Shi, 2-(Pyridin-2-yl)isopropyl (PIP) amine: An enabling directing group for divergent and asymmetric functionalization of unactivated methylene C(sp3)–H bonds, Accounts of Chemical Research. 54(12) (2021), 2750-2763. doi:10.1021/acs.accounts.1c00168
- R. Chang, Y. Chen, W. Yang, Z. Zhang, Z. Guo, Y. Li, Unveiling the mechanism, origin of stereoselectivity, and ligand-dependent reactivity in the Pd(II)-catalyzed unbiased methylene C(sp3)–H Alkenylation–Aza-Wacker Cyclization reaction, The Journal of Organic Chemistry. 85(20) (2020), 13191-13203. doi:10.1021/acs.joc.0c01906
- M. Borgini, P. Wipf, Stereoselective synthesis of δ-fluorinated isoleucines exploiting consecutive C(sp3)-H bond activations, Tetrahedron. 120 (2022), 132876. doi:10.1016/j.tet.2022.132876
- S. Garai, K.G. Ghosh, A. Biswas, S. Chowdhury, D. Sureshkumar, Diastereoselective palladium-catalyzed C(sp3)–H cyanomethylation of amino acid and carboxylic acid derivatives, Chemical Communications. 58(56) (2022), 7793-7796. doi:10.1039/D2CC03106J