Conjugate reduction of α,β-unsaturated carbonyl compounds catalyzed by a copper carbene complex

Organic Letters

Volumn 5, Issue 14, 2003, Pages 2417-2420

  Jurkauskas, Valdas ^a   Sadighi, Joseph P ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENOID; CARBONYL DERIVATIVE; CHLORIDE; COPPER CHLORIDE; COPPER COMPLEX; ESTER DERIVATIVE; IMIDAZOLE DERIVATIVE; KETONE DERIVATIVE; REDUCING AGENT; SILOXANE; SODIUM DERIVATIVE; WATER;

ARTICLE; CATALYST; CHEMICAL REACTION; CONJUGATE; REDUCTION; STOICHIOMETRY; SYNTHESIS;

CATALYSIS; COPPER; HYDROCARBONS; METHANE;

EID: 0141631426     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034560p     Document Type: Article

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20. Conjugate reductions using Cu-phosphine complexes: (a) Mahoney, W. S.; Stryker, J. M. J. Am. Chem. Soc. 1989, 111, 8818. (b) Lipshutz, B. H.; Keith, J.; Papa, P.; Vivian, R. Tetrahedron Lett. 1998, 39, 4627. (c) Mori, A.; Fujita, A.; Kajiro, H.; Nishihara, Y.; Hiyama, T. Tetrahedron 1999, 55, 4573. (d) Chiu, P.; Szeto, C.-P.; Geng, Z.; Cheng, K.-F. Org. Lett. 2001, 3, 1901. (e) Lipshutz, B. H.; Papa, P. Angew. Chem., Int. Ed. 2002, 41, 4580. Conjugate reductions using Cu with no ligand: (f) Ito, H.; Ishizuka, T.; Arimoto, K.; Miura, K.; Hosomi, A. Tetrahedron Lett. 1997, 38, 8887.
21. Conjugate reductions using Cu-phosphine complexes: (a) Mahoney, W. S.; Stryker, J. M. J. Am. Chem. Soc. 1989, 111, 8818. (b) Lipshutz, B. H.; Keith, J.; Papa, P.; Vivian, R. Tetrahedron Lett. 1998, 39, 4627. (c) Mori, A.; Fujita, A.; Kajiro, H.; Nishihara, Y.; Hiyama, T. Tetrahedron 1999, 55, 4573. (d) Chiu, P.; Szeto, C.-P.; Geng, Z.; Cheng, K.-F. Org. Lett. 2001, 3, 1901. (e) Lipshutz, B. H.; Papa, P. Angew. Chem., Int. Ed. 2002, 41, 4580. Conjugate reductions using Cu with no ligand: (f) Ito, H.; Ishizuka, T.; Arimoto, K.; Miura, K.; Hosomi, A. Tetrahedron Lett. 1997, 38, 8887.
22. Conjugate reductions using Cu-phosphine complexes: (a) Mahoney, W. S.; Stryker, J. M. J. Am. Chem. Soc. 1989, 111, 8818. (b) Lipshutz, B. H.; Keith, J.; Papa, P.; Vivian, R. Tetrahedron Lett. 1998, 39, 4627. (c) Mori, A.; Fujita, A.; Kajiro, H.; Nishihara, Y.; Hiyama, T. Tetrahedron 1999, 55, 4573. (d) Chiu, P.; Szeto, C.-P.; Geng, Z.; Cheng, K.-F. Org. Lett. 2001, 3, 1901. (e) Lipshutz, B. H.; Papa, P. Angew. Chem., Int. Ed. 2002, 41, 4580. Conjugate reductions using Cu with no ligand: (f) Ito, H.; Ishizuka, T.; Arimoto, K.; Miura, K.; Hosomi, A. Tetrahedron Lett. 1997, 38, 8887.
23. Conjugate reductions using Cu-phosphine complexes: (a) Mahoney, W. S.; Stryker, J. M. J. Am. Chem. Soc. 1989, 111, 8818. (b) Lipshutz, B. H.; Keith, J.; Papa, P.; Vivian, R. Tetrahedron Lett. 1998, 39, 4627. (c) Mori, A.; Fujita, A.; Kajiro, H.; Nishihara, Y.; Hiyama, T. Tetrahedron 1999, 55, 4573. (d) Chiu, P.; Szeto, C.-P.; Geng, Z.; Cheng, K.-F. Org. Lett. 2001, 3, 1901. (e) Lipshutz, B. H.; Papa, P. Angew. Chem., Int. Ed. 2002, 41, 4580. Conjugate reductions using Cu with no ligand: (f) Ito, H.; Ishizuka, T.; Arimoto, K.; Miura, K.; Hosomi, A. Tetrahedron Lett. 1997, 38, 8887.
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25. Available from Strem Chemicals, Inc.
26. Procedure for the preparation of 2. An oven-dried 25 mL Schlenk flask was charged with 0.900 g (2.12 mmol) of 1,3-bis(2,6-di-isopropylphenyl)imidazolium chloride, 0.210 g (2.12 mmol) of CuCl, 0.204 g (2.12 mmol) of NaOt-Bu, and 10.6 mL of dry THF. The resulting mixture was stirred for 4 h at room temperature. The reaction mixture was filtered over Celite, and the solvent was removed in vacuo. The product was dried under vacuum. NHC-CuCl (1) was obtained (0.774 g, 1.59 mmol, 75% yield) as a gray powder.
27. Addition of t-BuOH had an adverse effect on the rate of conjugate reduction of 3-phenethylcyclopentenone.
28. 4, and concentrated in vacuo. Purification by silica gel chromatography (hexanes/ethyl acetate 10:1) afforded 0.98 g (5.20 mmol, 88% yield) of 3-phenethylcyclopentanone (Table 3, entry 4) as a colorless oil.
29. For selected examples of in situ-generated N-heterocyclic carbene-transition metal catalysts, see: (a) Morgan, J. P.; Grubbs, R. H. Org. Lett. 2000, 2, 3153. (b) Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66, 3402. (c) Sato, Y.; Sawaki, R.; Mori, M. Organometallics 2001, 20, 5510. (d) Sémeril, D.; Bruneau, C.; Dixneuf, P. H. Adv. Synth. Catal. 2002, 344, 585 and references therein.
30. For selected examples of in situ-generated N-heterocyclic carbene-transition metal catalysts, see: (a) Morgan, J. P.; Grubbs, R. H. Org. Lett. 2000, 2, 3153. (b) Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66, 3402. (c) Sato, Y.; Sawaki, R.; Mori, M. Organometallics 2001, 20, 5510. (d) Sémeril, D.; Bruneau, C.; Dixneuf, P. H. Adv. Synth. Catal. 2002, 344, 585 and references therein.
31. For selected examples of in situ-generated N-heterocyclic carbene-transition metal catalysts, see: (a) Morgan, J. P.; Grubbs, R. H. Org. Lett. 2000, 2, 3153. (b) Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66, 3402. (c) Sato, Y.; Sawaki, R.; Mori, M. Organometallics 2001, 20, 5510. (d) Sémeril, D.; Bruneau, C.; Dixneuf, P. H. Adv. Synth. Catal. 2002, 344, 585 and references therein.
32. For selected examples of in situ-generated N-heterocyclic carbene-transition metal catalysts, see: (a) Morgan, J. P.; Grubbs, R. H. Org. Lett. 2000, 2, 3153. (b) Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66, 3402. (c) Sato, Y.; Sawaki, R.; Mori, M. Organometallics 2001, 20, 5510. (d) Sémeril, D.; Bruneau, C.; Dixneuf, P. H. Adv. Synth. Catal. 2002, 344, 585 and references therein.
33. See Supporting Information for a detailed procedure
34. 2O, and KOt-Bu in THF/toluene in the presence of PMHS, although much higher amounts of catalyst (2-5 mol %) were needed to effectively reduce trisubstituted α,β-unsaturated carbonyl compounds.
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37. For the formation of copper enolate intermediates in bis-phosphine-copper-catalyzed aldol reactions, see: Pagenkopf, B. L.; Krüger, J.; Stojanovic, A.; Carreira, E. M. Angew. Chem., Int. Ed. 1998, 37, 3124.
38. For evidence of silyl enol ether formation in analogous (bis-phosphine)CuH-catalyzed conjugate reductions, see refs 7b-d.
39. Similar rate enhancement using a bulky alcohol is observed in the (bis-phosphine)CuH-catalyzed conjugate reduction of α,β-unsaturated esters; see, ref 7f.