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1.
The synthesis of some 7-substituted-3-azabicyclo[3.3.1]nonanes is described. Routes followed were the debenzoylation of the 7-benzoyl derivative 7 and the decarboxylation of the 7-carboxy compounds 21 and 27. The so-obtained 7-oxo-N-tosyl-3-azabicyclo[3.3.1]nonanes 8and 11 show an extremely low reactivity towards a series of nucleophilic reagents. From analysis of the 1H NMR spectral data of a series of derivatives, the twin-chain conformation for the 7-exo compounds and the chair-boat conformation for the 7-endo compounds is indicated. 相似文献
2.
Condensation of 3-substituted 3-azabicyclo[3.3.1]nonan-9-ones with hydroxylamine and hydrazine hydrate gave the corresponding oximes, hydrazones, and azines. Reductive amination of the title compounds in the presence of sodium triacetoxyhydridoborate led to the formation of 3-substituted 3-azabicyclo[3.3.1]nonan-9-amines which were converted into the corresponding dihydrochlorides by treatment with dry hydrogen chloride. Treatment of 3-tert-butoxycarbonyl derivatives with HCl under analogous conditions was accompanied by elimination of the tert-butoxycarbonyl group to produce 3-azabicyclo[3.3.1]nonan-9-amine dihydrochlorides. 相似文献
3.
A. I. Moskalenko A. Yu. Chashchin V. I. Boev 《Russian Journal of Organic Chemistry》2011,47(7):1003-1010
Catalytic hydrogenation of 3-benzyl- and 3-tert-butoxycarbonyl-3-azabicyclo[3.3.1]nonan-9-one oximes over Raney nickel gave the corresponding 3-substituted 3-azabicyclo[3.3.1]nonan-9-amines
which were converted into amides via reactions with acetyl and chloroacetyl chlorides and maleic and succinic anhydrides,
into Schiff bases by condensation with benzaldehyde and 4-chlorobenzaldehyde, and into isothiocyanates by treatment with thiophosgene
in the presence of K2CO3. 3-Benzyl- and 3-tert-butoxycarbonyl-3-azabicyclo-[3.3.1]nonan-9-yl isothiocyanates readily reacted with methanol, aniline, and sodium azide to
produce methyl thiocarbamate, thiourea, and dihydrotetrazole-5-thione derivatives having a 3-azabicyclo[3.3.1]nonane fragment. 相似文献
4.
Yongjun Gao Haofan Wang Ronnie C. Mease Martin G. Pomper Andrew G. Horti 《Tetrahedron letters》2010,51(40):5333-5335
Improved syntheses of 7-methyl-2-exo-[3′-(2-bromopyridin-3-yl)-5′-pyridinyl]-7-azabicyclo[2.2.1]heptanes (3) and 7-methyl-2-exo-[3’-(6-bromopyridin-2-yl)-5′-pyridinyl]-7-azabicyclo[2.2.1]heptanes (4), precursors for PET radioligands [18F]XTRA (1) and [18F]AZAN (2), involving a key Stille coupling step followed by deprotection of Boc group and N-methylation are described. The new synthetic procedures provided the title compounds in more than 40% overall yields. 相似文献
5.
Yu. M. Atroshchenko I. E. Shakhkel'dyan O. Ya. Borbulevich A. N. Shchukin M. Yu. Antipin V. N. Khrustalev 《Russian Journal of Organic Chemistry》2005,41(11):1683-1689
Anionic hydride adduct of 1-(2-hydroxyethoxy)-2,4-dinitrobenzene was brought into a double Mannich condensation with formaldehyde and methylamine to furnish a mixture of isomeric 3-azabicyclo[3.3.1]nonanes: 3-methyl-6-(2-hydroxyethoxy)-1,5-dinitro-3-azabicyclo[3.3.1]non-6-ene and 3-methyl-6,6-ethylenedioxy-1,7-dinitro-3-azabicyclo[3.3.1]nonane. By means of NMR spectroscopy, X-ray difraction analysis, and quantum chemistry (PM3) we demonstrated that the spirocyclic isomer had chair-chair conformation with diequatorial orientation of substituents in positions 3 and 7. 相似文献
6.
Conformationally constrained spirofuropyridine analogues of epibatidine, syn-2 and anti-2, in which the 7-azabicyclo[2.2.1]heptane system and the 2-chloropyridine ring are held rigidly with the shorter and longer N-N distances, respectively, were synthesized from N-Boc-7-azabicyclo[2.2.1]heptan-2-one. The preliminary binding studies suggested that syn-2 has stronger binding affinity for nAChRs than anti-2. 相似文献
7.
Pyrolysis of 1,3,3-triméthyl-2-azabicyclo[2,2,2]octan-5-one-2-oxyl 5 leads to N-hydroxy-1,3,3-trimethyl-2-aza bicyclo[2,2,2]octan-5-one 6 and N-hydroxy-4,7,7-trimethyl-6-aza bicyclo[3,2,1]oct-3-ene-2-one 7. Under the same conditions, 1,3,3,7-anti-tetramethyl-2-aza bicyclo[2,2,2]octan-5-one-2-oxyl 9 leads to N-hydroxy-1,3,3,7-anti-tetraméthyl-2-aza bicyclo[2,2,2]octan-5-one 13 and N-hydroxy 4,5,7,7-tetramethyl-6-aza bicyclo[3,2,1]oct-3-ene-2-one 14, while 1,3,3,7-syn-tetramethyl-2-aza bicyclo[2,2,2]octan-5-one-1-oxyl 10 is stable. Kinetic studies show that the reaction proceeds by an autocatalytic process, probably involving an ionic mechanism. 相似文献
8.
Antonio J Moreno-VargasPierre Vogel 《Tetrahedron letters》2003,44(27):5069-5073
Enantiomerically pure 2,8-diazabicyclo[3.2.1]oct-2-ene derivatives (+)-5 and (−)-5 have been obtained from 2-azido-3-tosyl-7-azabicyclo[2.2.1]heptanes (+)-1 and (−)-2 and their enantiomers, by ring expansion under radical conditions. Compounds (+)-5 and (−)-5 were transformed into hemiaminals 9 ((3S,4R,5R)- and 10 ((3R,4S,5S)-5-(2-aminoethyl)-2,3,4-trihydroxypyrrolidine) that are good inhibitors of α-mannosidases. 相似文献
9.
S. G. Klepikova V. K. Yu E. E. Fomicheva R. D. Mukhasheva K. D. Praliev V. A. Solomin K. D. Berlin 《Chemistry of Heterocyclic Compounds》2003,39(10):1376-1384
Using the 1H NMR spectroscopic method it has been shown that 7-alkoxyalkyl-3-oxa-7-azabicyclo[3.3.1]nonan-9-ones and 7-alkoxyalkyl-3-oxa-7-azabicyclo[3.3.1]nonanes exist in deuterochloroform solution in a double chair conformation. 7-(3-Butoxypropyl)-3-oxa-7-azabicyclo[3.3.1]nonan-9-ol is a 1:1 mixture of the two stereoisomeric alcohols. One of them exists in a double chair conformation having an equatorial hydroxyl group with relation to the piperidine ring and the other in a chair-boat conformation having an axial hydroxyl group which involves an intramolecular hydrogen bond with the unshared electron pair of the nitrogen atom. 相似文献
10.
Carlos A.D. Sousa José E. Rodríguez-Borges Xerardo Garcia-Mera 《Tetrahedron letters》2008,49(40):5777-5781
The acid-catalyzed 1,4- and 1,3-cycloadditions between methyl glyoxylate oxime (1) and cyclopentadiene were investigated using various Lewis and/or Bronsted acids at different temperatures in dichloromethane as solvent. Besides the expected new adducts, (±)-methyl [(3-exo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylate (2) and (±)-methyl [(3-endo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylate (3), a third adduct, (±)-methyl (1R,4R,5R)-(2-oxa-3-azabicyclo[3.3.0]oct-7-ene)-4-carboxylate (4), whose formation can be explained by a 1,3-dipolar cycloaddition, was obtained. Yields and product ratios were found to be more dependent on the catalyst than on the temperature; these results and the stereochemistry of the adducts, confirmed by spectroscopic data (1H and 13C NMR) and by X-ray crystallography, were used to analyze and propose a mechanistic explanation for both cycloadditions. 相似文献
11.
The one-pot TiCl4 catalysed Diels–Alder/Mannich reaction of α-cyanoaminoacrylates with 2-silyloxy-1,4-butadienes gives 6-keto-3-azabicyclo[3.3.1]nonane-1-carboxylates. Reduction of the ketone and alkylation of the resultant alcohol gives 6-alkoxy-3-azabicyclo[3.3.1]nonanes mimicking the AE rings of a number of Delphinium and Aconitum alkaloids, with the same stereochemistry as the natural products. 相似文献
12.
Halichonic acid,a new rearranged bisabolene-type sesquiterpene from a marine sponge Halichondria sp.
Kenta Raiju Yuki Hitora Hikaru Kato Yuji Ise Esther D. Angkouw Remy E.P. Mangindaan Sachiko Tsukamoto 《Tetrahedron letters》2019,60(15):1079-1081
A new compound, halichonic acid (1), was isolated from a marine sponge Halichondria sp., together with (6R,7S)-7-amino-7,8-dihydro-α-bisabolene (2). The structure of 1 was elucidated by spectroscopic analysis and ECD spectrum calculation to be a rearranged bisabolene-type sesquiterpene having a 3-azabicyclo[3.3.1]nonene moiety. Compound 2 was cytotoxic against HeLa cells with an IC50 value of 50?μM, whereas 1 did not show cytotoxicity even at 50?μM. It is possible that 1 is biosynthesized from farnesyl pyrophosphate and glycine, with rearrangement. 相似文献
13.
The reduction of 3-benzyl- and 3-tert-butoxycarbonyl-3-azabicyclo[3.3.1]nonan-9-ones with sodium tetrahydridoborate gave the corresponding alcohols as mixtures of á- and ä-epimers at a ratio of 2: 3. The resulting alcohols reacted with acetyl chloride and methanesulfonyl chloride at the hydroxy group to form O-acetyl and O-methylsulfonyl derivatives. Reactions of the latter with potassium iodide and sodium azide afforded 3-substituted 9-iodo(azido)-3-azabicyclo[3.3.1]nonanes. 9-Iodo derivatives were treated with triphenylphosphine to obtain triphenylphosphonium salts which were converted into the corresponding phosphonium ylides by the action of sodium methoxide in methanol, and the ylides readily reacted with benzaldehyde according to Wittig. 相似文献
14.
V. K. Yu K. D. Praliev E. E. Fomicheva R. D. Mukhasheva S. G. Klepikova 《Chemistry of Heterocyclic Compounds》2006,42(4):512-519
New 7-alkoxyalkyl-3-thia-7-azabicyclo[3.3.1]nonan-9-ones were synthesized by the double Mannich cyclization of tetrahydrothiopyran-4-one
with suitable alkoxyalkylamines and paraformaldehyde in acetous methanol. Wolff-Kishner decarbonylation of these bicyclic
ketones gave 7-alkoxyalkyl-3-thia-7-azabicyclo[3.3.1]nonanes. The reduction of 7-alkoxyalkyl-3-thia-7-azabicyclo[3.3.1]nonan-9-ones
by alkali metal hydride complexes leads to a mixture of two stereoisomeric secondary alcohols, which are epimers at C(9). Active analgesic, antiarrhythmic, and antibacterial compounds were found among these products.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 585–592, April, 2006. 相似文献
15.
As a potential route to 9-functionalized-2-azabicyclo[3.3.1]nonanes we have investigated the silver nitrate catalyzed solvolysis of N-chloro-N-methyl-2-cyclohexene-1-ethanamine (4a) in methanol. By this route we obtained 1-methyl-7(a)-methoxy-cis-octahydroindole (5a), 1-methyl-7-chloro-cis-octahydroindole (6a), 2-methy (8a) in the approximate ratio of 75:1:3:23, respectively. The structure proofs of 5a and 8a were accomplished by chemical interrelating the two and by double resonance NMR spectroscopy, while the structures of 6a and 7a were assigned by mass spectroscopy. Appropriate deuterium studies substantiated the mass spectral fragmentation pathways. Mechanistically we favor the formation of the products by invoking the intermediacy of a nitrenium ion. 相似文献
16.
Yuko Otani Tetsuharu Hori Masatoshi Kawahata Kentaro Yamaguchi Tomohiko Ohwada 《Tetrahedron》2012,68(23):4418-4428
Homo-thiopeptides of bicyclic 7-azabicyclo[2.2.1]heptane-2-endo-carboxylic acid (Ah2c), which is a conformationally constrained β-proline mimic, were synthesized and their structures were investigated. These homo-thiopeptides showed a preference for ordered secondary structures with trans-thioamide bonds in the solid state and in solution. 相似文献
17.
The double Michael addition of benzylamine to 3-alkyl-2,7-cyclooctadienones, followed by hydrogenolysis, affords bridgehead substituted 9-azabicyclo[3.3.1]nonan-3-ones. Use of (+)-α-methylbenzylamine in the addition leads to mixtures of diastereomeric adducts in unequal amounts. Although the degree of asymmetric induction is low (10–20% ee), the diastereonomers can be easily separated, affording pure enantiomeric forms of the ladybug alkaloid adaline 1 and the Euphorbia alkaloid 3. 相似文献
18.
Thermal cyclization of cyclooctene-4-yl-carboxylic acid chloride (5) and cycloheptene-4-yl-carboxylic acid chloride (10) yielded mixtures of mainly endo and exo 2-chlorobicyclo[3.3.1]nonane-9-one (7 and 8), and mixtures of endo and exo 2-chlorobicyclo[3.2.1]octane-8-one (12 and 13), respectively. AlCl3-catalyzed cyclization of 10 gave the same product composition as the uncatalyzed reaction. In the AlCl3-catalyzed cyclization of 5 considerable amounts of bicyclo[3.3.1]non-2-en-9-one (6) and exo 3-chlorobicyclo[3.3.1]nonane-9-one (9) were obtained in addition to 7 and 8. 相似文献
19.
Condensation of N-substituted 3-azabicyclo[3.3.1]nonan-9-ones with difunctional N,N-, N,S-, and N,O-centered nucleophiles (o-phenylenediamine, 1,2-diphenylethane-1,2-diamine, 2-aminobenzenethiol, cysteine, 2-aminophenol, serine) gave the corresponding spiro heterocyclic compounds fused at the C9 atom. Treatment of N-tert-butoxycarbonyl-substituted spiro compounds with anhydrous hydrogen chloride resulted in elimination of the tert-butoxycarbonyl group with formation of spiro[3-azabicyclo[3.3.1]nonane-9,2′-azole] hydrochlorides. 相似文献
20.
I. Iriepa J. Bellanato F. J. Villasante E. Glvez A. Martín P. Gmez-Sal 《Journal of Molecular Structure》2004,708(1-3):117
A series of benzimidazole, thiazole and benzothiazole carbamates derived from 9-methyl-9-azabicyclo[3.3.1]nonan-3α-ol was synthesized and studied by 1H, 13C, 2D NMR and IR spectroscopy. To assist in the interpretation of the spectroscopic data, the crystal structure of 3 (9-methyl-9-azabicyclo[3.3.1]nonan-3α-yl 2-amino-1H-benzimidazole-1-carboxilate) was determined by X-ray diffraction. It has been found that 1-carbamates and 2-carbamates can be obtained in the case of the benzimidazole derivatives. The benzimidazole-1-carbamates are obtained in higher yields (41, 38%) than the benzimidazole-2-carbamates (3, 9%). The compounds studied displayed in CDCl3 solution a preferred chair–boat conformation with the substituted ring in a distorted boat form and the N–CH3 substituent in an axial position with respect to the chair piperidine ring. This conformation is similar to that determined by X-Ray diffraction for compound 3. 相似文献