Ritter reaction on terpenoids. IV. Remarkable tendency to produce 3-aza-bicyclo[3.3.1]non-2-ene systems from mono and sesquiterpenes

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Reaction of cyclic and acyclic monoterpenes with acetonitrile under Ritter type conditions was investigated. An unusual tendency to obtain racemic 8-acetamido-2,4,4,8-tetramethyl-3-aza-bicyclo [3.3.1] non-2-ene perchlorate was observed in all cases regardless of the starting terpene. It is worthy to...

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Autor principal: Rodriguez, J.B
Otros Autores: Gros, E.G, Caram, J.A, Marschoff, C.M
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: 1995
Acceso en línea:Registro en Scopus
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Biblioteca Central Dr. Luis F. Leloir (FCEN) de Universidad de Buenos Aires
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024 7 |2 scopus  |a 2-s2.0-0028868494 
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030 |a TELEA 
100 1 |a Rodriguez, J.B. 
245 1 0 |a Ritter reaction on terpenoids. IV. Remarkable tendency to produce 3-aza-bicyclo[3.3.1]non-2-ene systems from mono and sesquiterpenes 
260 |c 1995 
270 1 0 |m Rodriguez, J.B.; División Electroquímica, Institute de Investigaciones Fisicoquimicas Teóricas y Aplicadas (INIFTA), C.C. 16, Suc. 4, 1900 La Plata, Argentina 
506 |2 openaire  |e Política editorial 
504 |a Ritter, Minieri, (1948) J. Am. Chew. Soc., 70, p. 4045 
504 |a Krimen, Cota, (1969) Org. React., 17, p. 213 
504 |a Johnson, Madronero, (1966) Adv. Heterocycl. Chem., 6, p. 95 
504 |a Caram, Martins, Marschoff, Cafferata, Gros, (1984) Z. Naturforsch, 39 b, p. 972 
504 |a Samaniego, Baldessari, Ponce, Rodriguez, Gros, Caram, Marchoff, Ritter reaction on terpenoids. III. Stereospecific preparation of bicyclic [3.3.1] substituted piperidines (1994) Tetrahedron Letters, 35, p. 6967 
504 |a Caram, Rivero, Piro, Gros, Marschoff, On the unusual hydrolysis reaction of 8-acetamido-2,4,4,8-tetramethyl-3-azanium-bicyclo[3.3.1]non-2-ene perchlorate (1990) Canadian Journal of Chemistry, 68, p. 334 
504 |a Stoermer, Heathcock, (1993) J. Org. Chem., 58, p. 564 
504 |a Stevens, Kenney, Studies on the stereochemistry of nucleophilic additions to tetrahydropyridinium salts. Expeditious stereospecific total syntheses of (+)-makomakine, (+)-aristoteline, and (�)-hobartine (1983) Journal of the Chemical Society, Chemical Communications, p. 384 
504 |a Mirand, Massiot, Lévy, A synthetic entry in the Aristotelia alkaloids (1982) The Journal of Organic Chemistry, 47, p. 4170 
504 |a Delpech, Khuong-Huu, (1978) J. Org. Chem., 43, p. 4898 
504 |a Bick, Hai, (1985) The Alkaloids, 24. , For reviews of Aristotelia alkaloids see:, Chapter 3, A. Brossi, Academic Press, London 
504 |a Borschberg, (1991) Chimia, 45, p. 329 
504 |a Physical and spectroscopic properties were identical to the product obtained from (-)-β-pinene; For typical experimental procedures see ref 5. Compound (±)-3c,d. Foam. Yield = 80 %. IR (cm−1) = 3435, 2924, 2853, 1665, 1562, 1454, 1385, 1277, 1109, 625 M.S.* (m/z, %) = 304 (M+, 4); 393 (4); 261 (8); 244 (26); 222(21): 186(66); 108 (40); 84 (45); 43 (100) 1H-NMR (DMSO-d6, 200 MHz) δ = 1.37 (s, 3H, Me at C-4), 1.38 (s, 6H, Me at C-4 & C-8). 1.59. 1.62 (s, 3H. H-14); 1.65, 1.68 (s, 3H, Me at C-13); 1.87 (s, 3H, CH3CO); 2.49 (s, 3H, Me at C-2); 3.88 (m. 1H, H-1). 5.10 (m. 1H, H-12); 7.76 (s, 1H, NH); 13.51 (s, 1H, H+). 13C-NMR (DMSO-d6. 50 MHz) δ = 17.48. 17.58 (Me at C-12); 20.69 (CH3CO); 21.41, 22.41 (C-6); 22.63, 22.94 (C-7), 23.47, 25.00 (Me at C-5); 25.34, 26.75 (Me at C-12), 26.99, 27.10 (Me at C-8); 29.55, 31.15 (C-5), 31.42 (C-9); 35.14. 40.12 (C-10); [[Truncated]]; Harrison, Oliver, Cane, (1988) J. Am Chem. Soc., 110, p. 5922 
504 |a Cane, (1985) Acc. Chem. Res, 18, p. 220 
504 |a Rücker, Sesquiterpenes (1973) Angewandte Chemie International Edition in English, 12, p. 793 
504 |a Arigoni, Stereochemical aspects of sesquiterpene biosynthesis (1975) Pure and Applied Chemistry, 41, p. 219 
504 |a Ruzicka, In the Borderland between Bioorganic Chemistry and Biochemistry (1970) Annual Review of Biochemistry, 42, p. 1 
504 |a Shaw, Noble, Methyl (2R),(3S)-2,5-dimethyl-3-vinylhex-4-enoate (methyl santolinate) a new irregular monoterpene constituent of Artemesia tridentada tridentada (1975) Journal of the Chemical Society, Chemical Communications, p. 590 
504 |a It was expected that bisabolene was able to undergo cyclization because it presented structural similarities with terpinolene which gave 3a,b.4; m.p. = 170°C. [α]D = 0.0 (c 0.1, MeOH). I.R. (cm−1) = 3300, 2850, 1640, 1540, 1280, 1170, 1130, 950, 700, 680. M.S. (m/z, %) = 394 (M+. 1): 393 (4); 374 (5); 284 (9); 241 (59); 213 (39); 136 (34); 121 (46); 95 (100). 1H-NMR (DMSO-d6, 200 MHz) δ = 0.79 (s. 3H. Me-8); 0.81 (s, 3H, Me-10), 0.99 (s, 3H, Me 9); 1.20 (m. 2H, H-5); 1.40-1.75 (m, 4H. H-3a. H-4 & H-6). 1.95 (m. 1H. H-3b); 4 03 (m, 1H, H-2); 8.04 (d, J= 7.5 Hz, IH, -NH); 8.33 (m. 3H, aromatic protons) 13C-NMR (DMSO-d6. 50 MHz) δ = 11.44 (C-10); 19.80 (C-8)*; 20.31 (C-9)*. 26.72 (C-5): 35.59 (C-6); 44.32 (C-4); 46.48 (C-7), 49.66 (C-1), 57.42 (C-2). Aromatic signals are not listed due to strong coupling with fluorine atoms. *Signals could be interchanged. Anal. Calculated for C19H22NOF [[Truncated]]; Caram, Martins, Marschoff, Gros, (1986) Rev. Latinoamer. Quim., 17, p. 39 
504 |a Molecular modeling studies were performed with the program HyperChem (Autodesk, Inc., Sausalito, Ca) version 3.0 with the MM2 force field using the block-diagonal Newton Raphson mode to an RMS gradient of < 0.1 (max. 645 cycles) 
520 3 |a Reaction of cyclic and acyclic monoterpenes with acetonitrile under Ritter type conditions was investigated. An unusual tendency to obtain racemic 8-acetamido-2,4,4,8-tetramethyl-3-aza-bicyclo [3.3.1] non-2-ene perchlorate was observed in all cases regardless of the starting terpene. It is worthy to pointing out that when linear terpenes were used, the reaction is believed to follow a biomimetic pathway forming cyclic cationic species before reacting with the nitrile to form the same byciclic frame. If 3,5-ditrifluoromethylbenzonitrile was employed the corresponding isobornylamide derivative was obtained instead. © 1995 Elsevier Science Ltd.  |l eng 
536 |a Detalles de la financiación: Consejo Nacional de Investigaciones Científicas y Técnicas 
536 |a Detalles de la financiación: Acknowledgments. We thank UMYMFOR (CONICET) for partial financial support 
593 |a Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellon 2, Ciudad Universitaria, 1428 Buenos Aires, Argentina 
593 |a División Electroquímica, Institute de Investigaciones Fisicoquimicas Teóricas y Aplicadas (INIFTA), C.C. 16, Suc. 4, 1900 La Plata, Argentina 
690 1 0 |a 3 AZABICYCLO[3,3,1]NONANE DERIVATIVE 
690 1 0 |a BICYCLO[3.3.1]NONANE DERIVATIVE 
690 1 0 |a TERPENOID 
690 1 0 |a UNCLASSIFIED DRUG 
690 1 0 |a ARTICLE 
690 1 0 |a DRUG SYNTHESIS 
690 1 0 |a METHODOLOGY 
690 1 0 |a REACTION ANALYSIS 
690 1 0 |a STEREOCHEMISTRY 
700 1 |a Gros, E.G. 
700 1 |a Caram, J.A. 
700 1 |a Marschoff, C.M. 
773 0 |d 1995  |g v. 36  |h pp. 7825-7828  |k n. 43  |p Tetrahedron Lett.  |x 00404039  |w (AR-BaUEN)CENRE-415  |t Tetrahedron Letters 
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856 4 0 |u https://doi.org/10.1016/0040-4039(95)01671-4  |y DOI 
856 4 0 |u https://hdl.handle.net/20.500.12110/paper_00404039_v36_n43_p7825_Rodriguez  |y Handle 
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