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Synthesis and selected transformations of 2-unsubstituted 1-(adamantyloxy)imidazole 3-oxides: straightforward access to non-symmetric 1,3-dialkoxyimidazolium salts

Grzegorz Mlostoń, Małgorzata Celeda, Katarzyna Urbaniak, Marcin Jasiński, Vladyslav Bakhonsky, Peter R. Schreiner and Heinz Heimgartner

Beilstein J. Org. Chem. 2019, 15, 497–505. https://doi.org/10.3762/bjoc.15.43

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Synthesis and selected transformations of 2-unsubstituted 1-(adamantyloxy)imidazole 3-oxides: straightforward access to non-symmetric 1,3-dialkoxyimidazolium salts

Grzegorz Mlostoń, Małgorzata Celeda, Katarzyna Urbaniak, Marcin Jasiński, Vladyslav Bakhonsky, Peter R. Schreiner and Heinz Heimgartner

Beilstein J. Org. Chem. 2019, 15, 497–505. https://doi.org/10.3762/bjoc.15.43

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Mlostoń, G.; Celeda, M.; Urbaniak, K.; Jasiński, M.; Bakhonsky, V.; Schreiner, P. R.; Heimgartner, H. Beilstein J. Org. Chem. 2019, 15, 497–505. doi:10.3762/bjoc.15.43

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TY  - JOUR
A1  - Mlostoń, Grzegorz
A1  - Celeda, Małgorzata
A1  - Urbaniak, Katarzyna
A1  - Jasiński, Marcin
A1  - Bakhonsky, Vladyslav
A1  - Schreiner, Peter R.
A1  - Heimgartner, Heinz
T1  - Synthesis and selected transformations of 2-unsubstituted 1-(adamantyloxy)imidazole 3-oxides: straightforward access to non-symmetric 1,3-dialkoxyimidazolium salts
JF  - Beilstein Journal of Organic Chemistry
PY  - 2019///
VL  - 15
SP  - 497
EP  - 505
SN  - 1860-5397
DO  - 10.3762/bjoc.15.43
PB  - Beilstein-Institut
JA  - Beilstein J. Org. Chem.
UR  - https://doi.org/10.3762/bjoc.15.43
KW  - alkoxyamines
KW  - imidazole N-oxides
KW  - imidazolium salts
KW  - nucleophilic carbenes
KW  - sulfur transfer reaction
N2  - Adamantyloxyamine reacts with formaldehyde to give N-(adamantyloxy)formaldimine as a room-temperature-stable compound that exists in solution in monomeric form. This product was used for reactions with α-hydroxyiminoketones leading to a new class of 2-unsubstituted imidazole 3-oxides bearing the adamantyloxy substituent at N(1). Their reactions with 2,2,4,4-tetramethylcyclobutane-1,3-dithione or with acetic acid anhydride occurred analogously to those of 1-alkylimidazole 3-oxides to give imidazol-2-thiones and imidazol-2-ones, respectively. Treatment of 1-(adamantyloxy)imidazole 3-oxides with Raney-Ni afforded the corresponding imidazole derivatives without cleavage of the N(1)–O bond. Finally, the O-alkylation reactions of the new imidazole N-oxides with 1-bromopentane or 1-bromododecane open access to diversely substituted, non-symmetric 1,3-dialkoxyimidazolium salts. Adamantyloxyamine reacts with glyoxal and formaldehyde in the presence of hydrobromic acid yielding symmetric 1,3-di(adamantyloxy)-1H-imidazolium bromide in good yield. Deprotonation of the latter with triethylamine in the presence of elemental sulfur allows the in situ generation of the corresponding imidazol-2-ylidene, which traps elemental sulfur yielding a 1,3-dihydro-2H-imidazole-2-thione as the final product.
ER  -

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Nikolaenkova, E. B.; Grishchenko, S. Y.; Rybalova, T. V.; Tikhonov, A. Y. Preparation of 2-unsubstituted 5-aryl(hetaryl)-1-hydroxy-1H-imidazoles from of 4-aryl(hetaryl)-1-hydroxy-2,5-dihydro-1H-imidazole-2-carboxylic acid 3-oxides. Chemistry of Heterocyclic Compounds 2023, 59, 752–757. doi:10.1007/s10593-024-03268-5
Gladkikh, B. P.; Mokhov, V. M.; Butov, G. M.; Novakov, I. A. Reactions of 1,3-dehydroadamantane with polyfluorinated alcohols. Russian Chemical Bulletin 2023, 72, 664–668. doi:10.1007/s11172-023-3830-3
Singha, K.; Habib, I.; Hossain, M. Functionalization of imidazole N-oxide: a recent discovery in organic transformations. Beilstein journal of organic chemistry 2022, 18, 1575–1588. doi:10.3762/bjoc.18.168
Mlostoń, G.; Kowalczyk, M.; Celeda, M.; Jasiński, M.; Denel-Bobrowska, M.; Olejniczak, A. B. Fluorinated Analogues of Lepidilines A and C: Synthesis and Screening of Their Anticancer and Antiviral Activity. Molecules (Basel, Switzerland) 2022, 27, 3524. doi:10.3390/molecules27113524
Mlostoń, G.; Celeda, M.; Heimgartner, H.; Duda, D.; Obijalska, E.; Jasiński, M. Synthesis and Selected Transformations of 2-Unsubstituted Imidazole N-Oxides Using a Ball-Milling Mechanochemical Approach. Catalysts 2022, 12, 589. doi:10.3390/catal12060589
Bakhonsky, V. V.; Becker, J.; Mlostoń, G.; Schreiner, P. R. N-Alkoxyimidazolylidines (NOHCs): nucleophilic carbenes based on an oxidized imidazolium core. Chemical communications (Cambridge, England) 2022, 58, 1538–1541. doi:10.1039/d1cc05696d
Mlostoń, G.; Kowalczyk, M.; Celeda, M.; Gach-Janczak, K.; Janecka, A.; Jasiński, M. Synthesis and Cytotoxic Activity of Lepidilines A-D: Comparison with Some 4,5-Diphenyl Analogues and Related Imidazole-2-thiones. Journal of natural products 2021, 84, 3071–3079. doi:10.1021/acs.jnatprod.1c00797
Wróblewska, A.; Lauriol, G.; Mlostoń, G.; Bantreil, X.; Lamaty, F. Expedient synthesis of NOxy-Heterocyclic Carbenes (NOHC) ligands and metal complexes using mechanochemistry. Journal of Organometallic Chemistry 2021, 949, 121914. doi:10.1016/j.jorganchem.2021.121914
Mlostoń, G.; Celeda, M.; Poper, W.; Kowalczyk, M.; Gach-Janczak, K.; Janecka, A.; Jasiński, M. Synthesis, Selected Transformations, and Biological Activity of Alkoxy Analogues of Lepidilines A and C. Materials (Basel, Switzerland) 2020, 13, 4190. doi:10.3390/ma13184190
Mlostoń, G.; Celeda, M.; Jasiński, M.; Urbaniak, K.; Boratyński, P. J.; Schreiner, P. R.; Heimgartner, H. 2-Unsubstituted Imidazole N-Oxides as Novel Precursors of Chiral 3-Alkoxyimidazol-2-ylidenes Derived from trans-1,2-Diaminocyclohexane and Other Chiral Amino Compounds. Molecules (Basel, Switzerland) 2019, 24, 4398. doi:10.3390/molecules24234398

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