Navegar

Colección

Datos Estadísticas

Artículo

Estamos trabajando para incorporar este artículo al repositorio
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

The addition of organocuprates to α,β-unsaturated substrates, namely E-cinamaldehyde and 2-cyclohexen-1-one, was studied in THF. The furan moiety was chosen for the heterocuprate, because the methods for the synthesis of furan derivatives are scarce and they have a strong potentiality for tandem reactions. The performance of CuBr; CuBr.SMe2 and CuCN as copper precursors was examined: the higher yields of the 1,4-addition product were obtained using CuCN. The reaction with 2-cyclohexen-1-one gave the best results. In some cases, a compound that arises from dehydration of the 1,2-addition product was obtained and its yield increases near 70% when the reaction is carried out with furyl-lithium in the absence of any copper salt. Addition of up to 6 equivalents of TMSCl to the reaction mixture of 2-cyclohexen-1-one with furylcuprate at -78 C, leads to a clean addition yielding more than 90% of the 1,4-addition product. The only by-product is 2-TMS-furan. The absence of silylated ether of the enolate, is a strong evidence to rule out the cyclic intermediate or transition state that was previously proposed as the mechanism whereby TMSCl (acting as a Lewis base toward the cuprate) accelerates the reaction. Promoting conversion of the initially formed π-complex to a reactive tetravalent copper species is proposed instead. ©ARKAT-USA, Inc.

Registro:

Documento: Artículo
Título:Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive
Autor:Rodríguez, C.; Vázquez, Á.; Nudelman, N.S.
Filiación:Department of Organic Chemistry, Facultad de Ciencias Exactas Y Naturales, Pab. II, P. 3, 1428 Buenos Aires, Argentina
Palabras clave:Conjugated addition; Furyllithium; Organocuprates; TMSCl; α,β- unsaturated carbonyl compound
Año:2008
Volumen:2008
Número:6
Página de inicio:140
Página de fin:151
DOI: http://dx.doi.org/10.3998/ark.5550190.0009.613
Título revista:Arkivoc
Título revista abreviado:Arkivoc
ISSN:1551-701
CODEN:AGFUA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1551-701_v2008_n6_p140_Rodriguez

Referencias:

  • Daia, D.E., Gabbutt, C.D., Heron, B.M., Hepworth, J.D., Hursthouse, M.B., Malik, K.M.A., (2003) Tetrahedron Lett, 44, p. 1461
  • Krause, N., (2002) Modern Organocopper Chemistry, , Wiley-VCH: Weinheim
  • Bertz, S.H., Carlin, C.M., Deadwyler, D.A., Murphy, M.D., Oglew, C.A., Seagle, P.H., (2002) J. Am. Chem. Soc, 124, p. 13650
  • Dieter, R.K., Watson, R.T., Goswami, R., (2004) Org. Lett, 6, p. 253
  • Prat, D., Benedetti, F., Bouda, L.N., Girard, G.F., (2004) Tetrahedron Lett, 45, p. 765
  • Gree, R., Yadav, (2007) J. Chem. Rev, 107, p. 3286
  • Martynow, J., Jozwik, J., Szelejewski, W., (2007) Eur. J. Org. Chem, 4, p. 689
  • Park, O., Jung, J., (2007) Z. Naturforsch, 62 b, p. 556
  • Simonelli, F., Oliveira, A., Villar, J., Gariani, R., Wosch, C., Zarbin, P., (2007) Tetrahedron Lett, 48, p. 1507
  • Spiga, M., Secci, F., Piras, P., Ollivier, J., Frongia, A., Bernard, A., (2007) Tetrahedron, 63, p. 4968
  • Vila, C., Pedro, J., Muñoz, C., Molina, E., Fernandez, I., Blay, G., (2006) Tetrahedron, 62, p. 8069
  • Garcia, G.V., Nudelman, N.S., (2003) Org. Prep. & Proc. Int, 35, p. 445
  • Vazquez, A.; Goldberg, R.; Nudelman, N. S. In The Chemistry of Organolithium Compounds. Organolithiums as useful synthetic intermediates for tandem reactions; Rappaport Z.; Marek I. Eds.; Wiley: Chichester, 2005; 2, Chap. 2, pp. 63-137; Nicolau, K.C., Yue, E.W., Oshima, T., (2000) The New Chemistry. New Roads to Molecular Complexity, p. 178. , N. Hall, Ed, Cambridge University Press: Cambridge, U.K, Chap. 8, p
  • House, H.O., Respess, W.L., Whitesides, G.M., (1966) J. Org. Chem, 31, p. 3128
  • Whitesides, G.M., Fischer, W.F., San Filippo, R.W., Bashe, H.O., (1969) J. Am. Chem. Soc, 91, p. 4871
  • Lipshutz, B.H., Kayser, F., Liu, Z.-P., (1994) Angew. Chem. Int. Ed. Engl, 33, p. 1842
  • Lipshutz, B.H., Wood, M.R., (1994) J. Am. Chem. Soc, 116, p. 11689. , and refs. therein
  • Snyder, J.P., Bertz, S.H., (1995) J. Org. Chem, 60, p. 4312
  • Lipshutz, B.H., James, B., (1994) J. Org. Chem, 59, p. 7585
  • Boche, G., Bosol, F., Loherenz, J.C.W., (1994) Angew. Chem. Int. Ed. Engl, 33, p. 1161
  • Krause, N., (1999) Angew. Chem. Int. Ed. Engl, 38, p. 79
  • Corey, E.J., Posner, G.H., (1967) J. Am. Chem. Soc, 89, p. 3911
  • Corey, E.J., Posner, G.H., (1968) J. Am. Chem. Soc, 90, p. 5615
  • House, H.O., Chu, C.-Y., Wilkins, J.M., Umen, M.J., (1975) J. Org. Chem, 40, p. 1460
  • Bertz, S.H., Dabbagh, G., Williams, L.M., (1985) J. Org. Chem, 50, p. 4414
  • Corey, E.J., Boaz, N.W., (1985) Tetrahedron Lett, 26, p. 6015
  • Corey, E.J., Boaz, N.W., (1985) Tetrahedron Lett, 26, p. 6019
  • Corey, E.J., Hannon, F.J., Boaz, N.W., (1989) Tetrahedron, 45, p. 545
  • Kuwajima, I., Komatsu, M., Horiguchi, Y., (1989) Tetrahedron Lett, 30 (50), p. 7087
  • Bertz, S.H., Dabbagh, G., (1989) Tetrahedron, 45, p. 425
  • Bertz, S.H., Smith, R.A.J., (1990) Tetrahedron, 46, p. 4091
  • Lipshutz, B., Dimock, S., James, B., (1993) J. Am. Chem. Soc, 115, p. 9283
  • Snyder, J., Rossieter, B., Miao, G., Bertz, S., (1995) J. Am. Chem. Soc, 117, p. 11023
  • Shriver, D.F., (1989) The Manipulation of Air-Sensitive Compounds, , Wiley: New York
  • Vitale, A.A., Doctorovich, F., Nudelman, N.S., (1987) J. Organomet. Chem, 332, p. 9
  • Trzupek, L.S., Newirth, T.L., Kelly, E.G., Nudelman, N.S., Whitesides, G.M., (1973) J. Am. Chem. Soc, 95, p. 8118
  • Nudelman, N.S., Carro, C., (1999) Synlett, 12, p. 1942
  • NIST Data Center Collection (C) 2007 copyright by the U.S. Secretary of Commerce on behalf of the United States of America. All rights reserved; (2008) SDBSWeb, , http://riodb01.ibase.aist.go.jp/sdbs, May
  • Ng, J.S., Behling, J.R., Campbell, A.L., Nguyen, D., Lipshutz, B., (1988) Tetrahedron Lett, 29, p. 3045

Citas:

---------- APA ----------
Rodríguez, C., Vázquez, Á. & Nudelman, N.S. (2008) . Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive. Arkivoc, 2008(6), 140-151.
http://dx.doi.org/10.3998/ark.5550190.0009.613
---------- CHICAGO ----------
Rodríguez, C., Vázquez, Á., Nudelman, N.S. "Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive" . Arkivoc 2008, no. 6 (2008) : 140-151.
http://dx.doi.org/10.3998/ark.5550190.0009.613
---------- MLA ----------
Rodríguez, C., Vázquez, Á., Nudelman, N.S. "Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive" . Arkivoc, vol. 2008, no. 6, 2008, pp. 140-151.
http://dx.doi.org/10.3998/ark.5550190.0009.613
---------- VANCOUVER ----------
Rodríguez, C., Vázquez, Á., Nudelman, N.S. Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive. Arkivoc. 2008;2008(6):140-151.
http://dx.doi.org/10.3998/ark.5550190.0009.613