Abstract:
Treatment of chiral monoterpenes with different nitrile compounds in the presence of perchloric acid affords (1S,5R,8R) 8-alkyl(aryl)-2-alkyl(aryl)-2,4,4,8-tetramethyl-3-azabicyclo[3.3.1]non-2-ene or the corresponding (1R,5S,8S) enantiomer. The respective free imines yield optically pure piperidine derivatives when treated with reducing agents (NaBH4, NaCNBH3). © 1990.
Registro:
Documento: |
Artículo
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Título: | Ritter reaction on terpenoids. III. Stereospecific preparation of bicyclic [3.3.1] substituted piperidines |
Autor: | Samaniego, W.N.; Baldessari, A.; Ponce, M.A.; Rodriguez, J.B.; Gros, E.G.; Caram, J.A.; Marschoff, C.M. |
Filiación: | Departamento de Química Orgánica, Facultad de Ciencias Exactas, Universidad de Buenos Aires, Pabellon 2, Ciudad Universitaria, 1428 Buenos Aires, Argentina División Eletroquímica, Instutito de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), C.C. 16, Suc. 4, 1900 La Plata, Argentina
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Palabras clave: | alkaloid; piperidine derivative; terpenoid; article; drug synthesis; reaction analysis |
Año: | 1994
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Volumen: | 35
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Número: | 38
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Página de inicio: | 6967
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Página de fin: | 6970
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DOI: |
http://dx.doi.org/10.1016/0040-4039(94)88200-2 |
Título revista: | Tetrahedron Letters
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Título revista abreviado: | Tetrahedron Lett.
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ISSN: | 00404039
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CODEN: | TELEA
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00404039_v35_n38_p6967_Samaniego |
Referencias:
- Caram, Martins, Marschoff, Cafferata, Gros, (1984) Z. Naturforsch., 39 b, p. 972
- Ritter, Minieri, (1948) J. Am. Chem. Soc., 70, p. 4045
- Krimen, Cota, (1969) Org. React., 17, p. 213
- Johnson, Madroñero, (1966) Adv. Heterocycl. Chem., 6, p. 95
- 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
- Viturro, Rivero, Piro, Caram, Martins, Marschoff, Crystal and molecular structure of 8-acetamido-2,4,4,8-tetramethyl-3-azaniumbicyclo[3.3.1]non-2-ene perchlorate (1987) Canadian Journal of Chemistry, 65, p. 2000
- Bong, Ung, Craig, Scudder, Bishop, Ritter Reactions. V. Further Investigation of the 3-Azatricyclo[5.3.1.04,9]undec-2-ene System (1989) Australian Journal of Chemistry, 42, p. 1929
- Bishop, Hawkings, Ibana, (1988) J. Org. Chem., 53, p. 427
- A mixture of terpene (2 mmol) and nitrile (20 mmol) was warmed until melting was complete (when solid nitriles were employed) with vigorous stirring (starting materials and reaction temperatures are indicated in Table 1). Then, concentrated perchloric acid (0.1 ml) was added dropwise and the reaction mixture was stirred overnight at the same temperature. The mixture was allowed to cool and ethyl acetate (10 ml) was added. The white precipitate was filtered off and crystallized from ethanol. Yields fluctuated between 12–36%; 1(S),5(R),8(R)-8-Benzamido-2-phenyl-4,4,8-trymethyl-3-azabicyclo[3.3.1]non-2-ene (2a)mp = 210–212°C. [α]D = −231.5 (0.9, MeOH). IR (Nujol, cm−1) 3350, 2310, 1635, 1615, 1590, 1100, 735, 700, 620. 1H-NMR (DMSO-d6) δ 0.88 (s, 3H, CH3 at C-8), 1.50 (s, 3H, CH3 at C-4), 1.61 (s, 3H, CH3 at C-4), 1.70–2.20 (bs, 8H, H-1, H-5, H-6, H-7 & H-9), 5.03 (bs, 1H, CNH+), 7.40–8.16 (m, 10H, aromatic protons). 13C-NMR (DMSO-d6) δ 21.65 (CH3 at C-4), 23.26 (CH3 at C-4), 25.66 (C-7), 28.50 (C-6 and Me at C-8), 31.28 (C-9), 33.51 (C-5), 38.83 (C-1), 56.37 (C-8), 62.13 (C-4), 127.28 (Ph), 127.93 (Ph), 128.89 (Ph), 128.96 (Ph), 129.24 (Ph), 131.03 (Ph), 133.08 (Ph), 133.30 (Ph), 134.35 (Ph), 134.98 (Ph), 167.23, PhC[[Truncated]]; Harada, (1970) The Chemistry of the Carbon-Nitrogen Double Bond, pp. 276-293. , S. Patai, Wiley, New York
- Anderson, Robertson, Avey, Donovan, Bick, Bremner, Finney, Russell, Aristoteline, a novel indole alkaloid: X-ray structural determination (1975) Journal of the Chemical Society, Chemical Communications, p. 511. , These synthetic compounds are closely related to naturally occurring alkaloids, for example, aristoteline, isolated from Aristotelia serrata, Aristotelia peduncularis and from the leaves and stems of Aristotelia chilensis
- Kyburz, Schöpp, Bick, Hesse, (1981) Helv. Chim. Acta, 64, p. 2555
- Bhakuni, Silva, Matlin, Sammes, (1976) Phytochemistry, 15, p. 574
- Bick, Hai, Preston, Gallagher, (1980) Tetrahedron Lett., 21, p. 545. , aristotelinona, isolated from A. serrata
- Kyburz, Schöpp, Hesse, Peduncularistin, Triabunnin und Aristolarin, drei neue Indolalkaloide ausAristotelia peduncularis (LABILL.) HOOK. F., 191. Mitteilung �ber organische Naturstoffe (1984) Helvetica Chimica Acta, 67, p. 804. , tasmanine, isolated from A. peduncularis12b; serratoline, isolated from A. serrata
- Kyburz, Schöpp, Bick, Hesse, (1979) Helv. Chim. Acta, 62, p. 2539. , hobartine, isolated from A. peduncularis
Citas:
---------- APA ----------
Samaniego, W.N., Baldessari, A., Ponce, M.A., Rodriguez, J.B., Gros, E.G., Caram, J.A. & Marschoff, C.M.
(1994)
. Ritter reaction on terpenoids. III. Stereospecific preparation of bicyclic [3.3.1] substituted piperidines. Tetrahedron Letters, 35(38), 6967-6970.
http://dx.doi.org/10.1016/0040-4039(94)88200-2---------- CHICAGO ----------
Samaniego, W.N., Baldessari, A., Ponce, M.A., Rodriguez, J.B., Gros, E.G., Caram, J.A., et al.
"Ritter reaction on terpenoids. III. Stereospecific preparation of bicyclic [3.3.1] substituted piperidines"
. Tetrahedron Letters 35, no. 38
(1994) : 6967-6970.
http://dx.doi.org/10.1016/0040-4039(94)88200-2---------- MLA ----------
Samaniego, W.N., Baldessari, A., Ponce, M.A., Rodriguez, J.B., Gros, E.G., Caram, J.A., et al.
"Ritter reaction on terpenoids. III. Stereospecific preparation of bicyclic [3.3.1] substituted piperidines"
. Tetrahedron Letters, vol. 35, no. 38, 1994, pp. 6967-6970.
http://dx.doi.org/10.1016/0040-4039(94)88200-2---------- VANCOUVER ----------
Samaniego, W.N., Baldessari, A., Ponce, M.A., Rodriguez, J.B., Gros, E.G., Caram, J.A., et al. Ritter reaction on terpenoids. III. Stereospecific preparation of bicyclic [3.3.1] substituted piperidines. Tetrahedron Lett. 1994;35(38):6967-6970.
http://dx.doi.org/10.1016/0040-4039(94)88200-2