Cyclizations of α-diketones to α-hydroxycyclopentenones on silica gel in the absence of solvent

Synthesis

Volumn , Issue 13, 2006, Pages 2139-2142

  Uhrich, Elizabeth A ^a   Batson, William A ^a   Tius, Marcus A ^a,b  

^a UNIVERSITY OF HAWAII   (United States)

^b UNIVERSITY OF HAWAII CANCER CENTER   (United States)

Author keywords

Cyclizations; Diketones; Nazarov reactions; Rearrangements; Silica gel

Indexed keywords

AMINES; AROMATIZATION; REACTION KINETICS; SILICA GEL; SOLVENTS; UNSATURATED COMPOUNDS;

CYCLIZATIONS; DIKETONES; NAZAROV REACTIONS; REARRANGEMENTS;

KETONES;

1,2 DICARBONYL DERIVATIVE; 5 BENZYL 2 HYDROXY 3 METHYL 4 PHENYLCYCLOPENT 2 ENONE; ALPHA HYDROXYCYCLOPENTENONE; CYCLOPENTENONE DERIVATIVE; SILICA GEL; TRIETHYLAMINE; UNCLASSIFIED DRUG;

ARTICLE; BIOMASS; CHEMICAL STRUCTURE; COLUMN CHROMATOGRAPHY; CYCLIZATION; DIASTEREOISOMER; FERMENTATION; HYDROGEN BOND; ISOMERIZATION; MICHAEL ADDITION; ROOM TEMPERATURE; THIN LAYER CHROMATOGRAPHY;

EID: 33746039261     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2006-942420     Document Type: Article

References (18)

1. Batson, W. A.; Sethumadhavan, D.; Tius, M. A. Org. Lett. 2005, 7, 2771.
2. (a) Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734.
3. (b) Baldwin, J. E.; Cutting, J.; Dupont, W.; Kruse, L.; Silberman, L.; Thomas, R. C. J. Chem. Soc., Chem. Commun. 1976, 736.
4. (c) Baldwin, J. E.; Kruse, L. I. J. Chem. Soc., Chem. Commun. 1977, 233.
5. (d) Baldwin, J. E.; Thomas, R. C.; Kruse, L. I.; Silberman, L. J. Org. Chem. 1977, 42, 3846.
6. Forest, J.; Bee, C.; Cordaro, F.; Tius, M. A. Org. Lett. 2003, 5, 4069.
7. Dhoro, F.; Tius, M. A. J. Am. Chem. Soc. 2005, 127, 12472.
8. Hashmi, A. S. K.; Bats, J. W.; Choi, J.-H.; Scharz, L. Tetrahedron Lett. 1998, 39, 7491.
9. Many reactions can be conducted on solid supports in the absence of solvent; for recent reviews, see: (a) Loupy, A. Top. Curr. Chem. 1999, 206, 153.
10. (b) Tanaka, K. Solvent-Free Organic Synthesis; Wiley-VCH: Weinheim, 2003.
11. Professor Marvin J. Miller (Notre Dame) had suggested that a trace metal oxide present as a contaminant in silica gel, possibly iron, was responsible for catalyzing the cyclization reaction. The silica gel manufacturer's (Natland International Corporation) certificate of analysis indicated 'less than 0.02% iron' (<200 ppm) and our independent determination (Desert Analytics) indicated 0.03% (300 ppm) iron. Iron is certainly present, probably as Fe(III) oxide; therefore we cannot exclude this possibility.
12. The Nazarov reaction has been reviewed: (a) Habermas, K. L.; Denmark, S.; Jones, T. K. Org. React. 1994, 45, 1.
13. (b) Tius, M. A. Acc. Chem. Res. 2003, 36, 284.
14. (c) Harmata, M. Chemtracts 2004, 17, 416.
15. (d) Frontier, A.; Collison, C. Tetrahedron 2005, 61, 7577.
16. (e) Pellissier, H. Tetrahedron 2005, 61, 6479.
17. (f) Tius, M. A. Eur. J. Org. Chem. 2005, 2193.
18. Ding, G.; Song, Y. C.; Chen, J. R.; Xu, C.; Ge, H. M.; Wang, X. T.; Tan, R. X. J. Nat. Prod. 2006, 69, 302.