Synthesis of N-(adamantan-1-yl)amides by reaction of carboxylic acid amides with 1-bromo(chloro)adamantane catalyzed by manganese compounds

Хуснутдинов, Р. И.; Shchadneva, N. А.; Khisamova, L. F.

doi:10.1134/s107042801504003x

Cited by 5 publications

(3 citation statements)

References 6 publications

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“…Along with well-known and comprehensively studied adamantyl-containing amines, amantadine and rimantadine, antiviral activity has been found for adamantylated azoles, amides, sulfamides, urethanes, and some other types of compounds. In addition, adamantylated nitrogencontaining compounds are of interest as intermediates for the synthesis of other compounds with practically valuable properties.The known methods for the preparation of these compounds consist in adamantylation of various N-nucleophiles with adamantane, 1-haloadamantanes, or 1-adamantanol in the presence of Lewis or Brønsted acid, i.e., under conditions favoring the formation of 1-adamantyl cation.For example, N-adamantylation of amides was proposed to be carried out using manganese catalysts (Figure 1), among which dimanganesedecacarbonyl showed the best results to give target compounds in a yield up to 94% [2]. In the trifluoroacetic acid medium (Figure 2), the adamantylation of carboxylic acid amides can be carried out with different efficiency upon long-term reflux [3,4].…”

Section: Introductionmentioning

confidence: 99%

Aluminum Triflate—Catalyzed Adamantylation of N-Nucleophiles

Коншин¹,

Shcherbinin²,

Lupanova³

et al. 2018

22nd International Electronic Conference on Synthetic Organic Chemistry

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An efficient method is proposed for N-adamantylation of primary carboxamides and sulfonamides, ethyl carbamate, and 4-nitroaniline using the stoichiometric amount of 1-adamantanol in the presence of 5 mol% aluminum triflate in nitromethane. Similarities and differences between adamantylation of some azoles catalyzed by aluminum triflate in nitromethane and the reaction catalyzed by Brønsted acids were revealed.

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Section: Introductionmentioning

confidence: 99%

Aluminum Triflate—Catalyzed Adamantylation of N-Nucleophiles

Коншин¹,

Shcherbinin²,

Lupanova³

et al. 2018

22nd International Electronic Conference on Synthetic Organic Chemistry

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“…We have recently shown that the Mn-catalyzed reaction of 1-bromoadamantane with carboxylic acid amides produced N-(adamantan-1-yl)amides in yields of 70-90% [10].…”

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confidence: 99%

“…The reactions were carried out as described previously [10]. The interaction of 1-bromo-3,5-dimethyladamantane I with formamide, acetamide, propionamide, and benzamide in the presence of Mn 2 (СО) 10 [or MnCl 2 , MnBr 2 , Mn(OAc) 2 , Mn(acac) 3 ] resulted in the formation of the corresponding N-(3,5-dimethyladamant-1-yl)amides II-V in 78-99% yield. At the same time the nature and the structure of the organic amide had no significant effect on the selectivity of the reaction and the yield of adamantylamide (Scheme 1).…”

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confidence: 99%

Amidation of 1-bromo-3,5-dimethyladamantane catalyzed with manganese compounds and complexes

2015

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One of the most important compounds containing adamantane moiety are amides like 1-acetamido-3,5dimethyladamantane, whose deprotection gives 1amino-3,5-dimethyladamantane, the constituent of Memantine drug. Memantine is unique pharmaceutical preparation effective for the treatment of Alzheimer's disease and other CNS disorders at an early stage. It helps to normalize the psychic activity of human: it improves memory and ability to concentrate, reduces fatiguability, depression symptoms, and restores neuromuscular system disorders [1][2][3][4][5].Typically 1-bromo-3,5-dimethyladamantane I is used for laboratory and industrial synthesis of various N-(adamant-1-yl)amides by Ritter method [6,7]. Known methods for producing N-(adamant-1-yl)acylamides include reacting 1-bromoadamantane with formamide and acetamide at elevated temperature (185±195°C) [8], or in the presence of the stoichiometric amount of silver sulfate as the catalyst [9]. Yields of amides in both cases do not exceed 45%.Considering the practical importance of N-(3,5-dimethyladamantane-1-yl)amides, we aimed at developing a new effective method for their preparation using metal complex catalysts. We have recently shown that the Mn-catalyzed reaction of 1-bromoadamantane with carboxylic acid amides produced N-(adamantan-1-yl)amides in yields of 70-90% [10].In the present work, we found that manganese compounds and complexes catalyzed amidation of 1bromo-3,5-dimethyladamantane I with carboxylic acid amides. The reactions were carried out as described previously [10]. The interaction of 1-bromo-3,5-dimethyladamantane I with formamide, acetamide, propionamide, and benzamide in the presence of Mn 2 (СО) 10 [or MnCl 2 , MnBr 2 , Mn(OAc) 2 , Mn(acac) 3 ] resulted in the formation of the corresponding N-(3,5-dimethyladamant-1-yl)amides II-V in 78-99% yield. At the same time the nature and the structure of the organic amide had no significant effect on the selectivity of the reaction and the yield of adamantylamide (Scheme 1).In summary, the Mn-containing catalysts made it possible to perform amidation of 1-bromo-3,5-dimethyladamantane I with organic amides in a single step in a solvent-free conditions.[Mn] = MnCl 2 , MnBr 2 , Mn(OAc) 2 , Mn(acac) 3 , Mn 2 (CO) 10 ; R = H (II), CH 3 (III), C 2 H 5 (IV), Ph (V). + RCONH 2 [Mn] 3 mol % 120−130 o C, 2−3 h, 78−100% NHCOR Br I I I −V Scheme 1.

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Metal complex catalysis in the chemistry of lower diamondoids

Хуснутдинов¹,

Shchadneva²

2019

Russ. Chem. Rev.

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The review presents the first survey of published data on the use of compounds, complexes and nanoparticles of transition metals (Fe, Co, Ni, Mn, V, Mo, Cu, Pd, Pt, Rh, Ru, Os, Au, Re and Th) in the catalytic transformations of lower diamondoids — adamantane, diamantane and their derivatives. Catalytic halogenation, oxidation, alkylation and cross-coupling reactions are considered, and the formation pathways of C–N, C–S and C–Se bonds in the series of adamantanoids are discussed. Reaction conditions, appropriate catalytic systems and the structures of products are presented. The bibliography includes 242 references.

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Synthesis of N-(adamantan-1-yl)amides by reaction of carboxylic acid amides with 1-bromo(chloro)adamantane catalyzed by manganese compounds

Abstract: N-(Adamantan-1-yl)amides were synthesized in 70-90% yield by reaction of 1-bromoadamantane with carboxylic acid amides in the presence of manganese salts and complexes.

Cited by 5 publications

References 6 publications

Aluminum Triflate—Catalyzed Adamantylation of N-Nucleophiles

Aluminum Triflate—Catalyzed Adamantylation of N-Nucleophiles

Amidation of 1-bromo-3,5-dimethyladamantane catalyzed with manganese compounds and complexes

Metal complex catalysis in the chemistry of lower diamondoids

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