Chemo-enzymatic synthesis of chiral cyclic compounds: Efficient kinetic resolution of 2-bromo-2-cyclohexenol

Tetrahedron Asymmetry

Volumn 7, Issue 10, 1996, Pages 2801-2804

  Noheda, Pedro ^a   Garciá, Germán ^a   Pozuelo, M Carmen ^a   Herradón, Bernardo ^a  

^a INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

2 BROMO 2 CYCLOHEXENOL; CYCLOALKANOL DERIVATIVE; ORGANOBROMINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; DRUG STRUCTURE; DRUG SYNTHESIS; PRIORITY JOURNAL;

EID: 0030272813     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/0957-4166(96)00366-7     Document Type: Article

References (21)

1. (1) Noheda, P.; Garcia, G.; Pozuelo, C. Manuscript in preparation.
2. (2) Seebach, D.; Herradón, B. Tetrahedron Lett. 1987, 28, 3791-3794
3. (3) Herradón, B. Helv. Chim. Acta 1988, 71, 977-980. Herradón, B. Seebach, D. Helv. Chim. Acta 1989, 72, 690-714.
4. (3) Herradón, B. Helv. Chim. Acta 1988, 71, 977-980. Herradón, B. Seebach, D. Helv. Chim. Acta 1989, 72, 690-714.
5. (4) Enzyme Catalysis in Organic Synthesis. A Comprehensive Handbook; Drauz, K.; Waldmann, H., Eds.; VCH: Weinheim; 1995; pp 165-271.
6. (5) Ors, M.; Morcuende, A.; Jiménez-Vacas, M.-I.; Valverde, S.; Herradón, B. Synlett 1996, 449-451.
7. (6) The advantages of this methodology have been previously discussed, see: Herradón, B.; Valverde, S. Tetrahedron: Asymmetry 1994, 5, 1479-1500.
8. (7) Compounds of class 6 would be accesible through: a) sequential halogen-lithium exchange and reaction with electrophiles; b) transition-metal catalyzed nucleophilic substitution of the bromine atom; c) Pd(O) catalyzed carbonylation or alkoxycarbonylation. Cyclohexene derivatives of type 7 might be prepared through: d) Claisen rearrangement; e) Wittig rearrangement; and f) Pd(0)-catalyzed allylic substitution. g) Other synthetically useful applications would be the reactions of the double bond, including hydrogenation, hydroboration, hydrosilylation, and bis-hydroxylation, among others. Due to the steric and electronic bias of these molecules, these reactions are expected to be highly regio- and stereo-selective. For selected references on all these subjects, see Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford; 1991.
9. (8) Corey, E. J.; Reichardt, G. A. Tetrahedron Lett. 1989, 30, 5547-5550.
10. (9) Ito, S.; Kasai, M.; Ziffer, H.; Silverton, J. V. Can. J. Chem. 1987, 65, 574-582.
11. (10) Johnson, C. R.; Sakaguchi, H. Synlett 1992, 813-816.
12. (11) (±)-1 and (±)-14 have been prepared from cyclopentene and cyclohexene, respectively, as reported in: Sandler, S. S. J. Org. Chem. 1967, 32, 3876-3881).
13. (12) Sih, C. J.; Wu, S. H. Topics Stereochem. 1989, 79, 63-125.
14. 3, c = 0.87) for a sample reported to be 87%ee].
15. a Isabel Jiménez (Instituto de Química Orgánica General, C. S. I. C.), to whom we thank for her assistance on the glc analysis.
16. (15) The recovered enzyme can be reused; although the activity is slightly lower than in the original experiment, the selectivity is of the same order.
17. (16) Approximately the same selectivity and velocity are observed using wet toluene or vinyl acetate as solvents.
18. (17) Similar selectivity has been achieved when the reaction has been carried out with 6000 units of PPL per mmol.
19. (18) When PFL or AA-I are the biocatalyst, low enantioselective transformations are also observed.
20. (19) Palmisano, G.; Santagostino, M.; Riva, S.; Sisti, M. Tetrahedron: Asymmetry 1995, 6, 1229-1232.
21. (20) Financial support from DGICYT (Project numbers PB-93-0154, PB-94-0104, and PB-95-0065) is gratefully acknowledged.