Synthesis of Polysantol® and related sandalwood-type odorants using magnesium α-bromoketone enolates

Tetrahedron Letters

Volumn 45, Issue 12, 2004, Pages 2619-2622

  Castro, Juan M ^a   Linares Palomino, Pablo J ^a   Salido, Sofía ^a   Altarejos, Joaquín ^a   Nogueras, Manuel ^a   Sánchez, Adolfo ^a  

^a UNIVERSITY OF JAÉN   (Spain)

Author keywords

Bromoketones; Campholenic aldehyde; Aldol reaction; Magnesium enolates; Odorants; Polysantol ; Sandalwood

Indexed keywords

BROMINE DERIVATIVE; DEODORANT AGENT; KETONE DERIVATIVE; MAGNESIUM DERIVATIVE; PERFUME;

ALDOL REACTION; ARTICLE; DEWATERING; METHODOLOGY; MOLECULE; QUANTUM YIELD; REDUCTION; SYNTHESIS;

SANTALACEAE;

EID: 1542332375     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2004.01.142     Document Type: Article

References (19)

1. Shankaranarayana K.H., Parthasarathi K. Perfum. Flavor. 9:1984;17-20.
2. Fráter G., Bajgrowicz J.A., Kraft P. Tetrahedron. 54:1998;7633-7703.
3. Schulte-Elte, K.-H.; Muller, B. L.; Pamingle, H. EP155591 (Priority, 23 March 1984, to Firmenich S.A.) [Chem. Abstr. 1985, 105, 191435q].
4. Linares-Palomino P.J., Salido S., Altarejos J., Sánchez A. Tetrahedron Lett. 44:2003;6651-6655.
5. Castro J.M., Salido S., Altarejos J., Nogueras M., Sánchez A. Tetrahedron. 58:2002;5941-5949.
6. ® from α-pinene, 23rd International Symposium on the Chemistry of Natural Products, Florence, 2002; p 135.
7. Castro, J. M.; Salido, S.; Altarejos, J.; Nogueras, M.; Sánchez, A. One step preparation of (+)-norambreinolide from sclareol oxide, 23rd International Symposium on the Chemistry of Natural Products, Florence, 2002; p 164.
8. Palomino, F. M.; Salido, S.; Altarejos, J.; Nogueras, M.; Sánchez, A. Synthesis of potential fragrance compounds from davanone, a natural odourless tetrahydrofuran derivative, 23rd International Symposium on the Chemistry of Natural Products, Florence, 2002; p 299.
9. Linares P., Salido S., Altarejos J., Nogueras M., Sánchez A. Chlorosulfonic acid as a cyclization agent for preparing cyclic ether odorants. Lanzotti V., Taglialatela-Scafati O. Flavour and Fragrance Chemistry. 2000;101-107 Kluwer Academic, Dordrecht.
10. The starting material 1 used in this work had a specific rotation of -2.2, which corresponds to an optical purity of ca. 60% ((S)-1 / (R)-1 4:1). This means that all compounds obtained from 1 in this work are nonracemic mixtures of stereoisomers on which studies to determine configurations have not been carried out.
11. The direct conventional aldol reaction of α-campholenic aldehyde 1 and 3-methyl-2-butanone 6 was previously carried out yielding the β-hydroxyketone 8 in 32% yield, along with important amounts of unreacted starting material and other compounds resulting from the alternative aldol reaction attack of 6 (C-1) to 1.
12. Fellmann P., Dubois J.-E. Tetrahedron. 34:1978;1349-1357. and references cited therein.
13. 4. After removing the solvent on a rotary evaporator the residue was purified by reduced pressure distillation to yield the corresponding α-bromoketone.
14. 4. After removing the solvent on a rotary evaporator the residue was purified by silica gel column chromatography to yield the corresponding β-hydroxyketone. For compounds 19 and 20, an α-bromoketone/ 1 ratio of 6:5 and more concentrated solutions were used in order to achieve better results.
15. 4. Evaporation of the solvent on a rotary evaporator yielded the corresponding enone.
16. 4. Evaporation of the solvent on a rotary evaporator yielded the corresponding enone.
17. Bolster M.G., Jansen B.J.M., de Groot A. Tetrahedron. 57:2001;5663-5679.
18. Naipawer, R. E. EP 203528 (Priority, 31 May 1985, to Givaudan Co.) [Chem. Abstr. 1987, 106, 175828].
19. A report of the use of similarly-derived magnesium enolates in the regioselective addition to enones is: Bertrand J., Gormchon L., Mahoni P. Tetrahedron. 40:1984;4127-4140.