Two methods for the preparation of 2-cyclohexenones from resin-bound 1,3-cyclohexanedione

Tetrahedron Letters

Volumn 38, Issue 19, 1997, Pages 3365-3368

  Fraley, Mark E ^a   Rubino, Robert S ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 CYCLOHEXENONE DERIVATIVE;

ARTICLE; DRUG PURITY; DRUG SYNTHESIS; IN VITRO STUDY; INFRARED SPECTROPHOTOMETRY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS;

EID: 0031008230     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00631-X     Document Type: Article

References (13)

1. For recent reviews, see (a) Thompson, L.A.; Ellman, J. A. Chem. Rev. 1996, 96, 555-600.
2. (b) Fruchtel, J.S.; Jung, G. Ang. Chem. Int. Ed. Eng. 1996, 35, 17-42.
3. (c) Hermkens, P. H. H.; Ottenheijm, H. C. J.; Rees, D. Tetrahedron 1996, 52, 4527-4554.
4. Very few 3-substituted-2-cyclohexenones are commercially available despite their importance as building blocks in organic synthesis.
5. 1H NMR, FTIR, and HRMS spectra. Reactions were performed on approximately 200 mg of resin to afford 10-30 mg of enone. The Grignard addition sequence is amenable to scale-up: the reaction of entry 5 (Table 1) was performed using 2.0 g of resin 1 and furnished 230 mg of 3-(p-tolyl)-2-cyclohexenone (84% yield).
6. McMurry, J. E.; Scott, W. J.; Tetrahedron Lett. 1983, 24, 979-982.
7. Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981, 11, 513-519.
8. The lower yields in the Suzuki cross-coupling pathway may be attributed in part to incomplete conversion of 1 to 4. Prolonged exposure of 5 to the cleavage conditions failed to afford additional enone product.
9. For solid-phase Suzuki cross-coupling reactions of aryl iodides and bromides, see (a) Frenette, R.; Friesen, R. W. Tetrahedron Lett. 1994, 35, 9177-9180.
10. (b) Backes, B. J.; Ellman, J. A. J. Am. Chem. Soc. 1994, 116, 11171-11172.
11. (c) Guiles, J. W.; Johnson, S. G.; Murray, W. V. J. Org. Chem. 1996, 61, 5169-5171.
12. For solid-phase Heck reactions of aryl iodides and bromides, see (a) Yu, K-L.; Deshpande, M. S.; Vyas, D. M. Tetrahedron Lett. 1994, 35, 8919-8922.
13. (b) Goff, D. A.; Zuckermann, R. N. J. Org. Chem. 1995, 60, 5748-5749.