A practical synthesis of enantiopure (R)-4-hydroxy-2-cyclohexen-1-one

Liebigs Annales

Volumn , Issue 10, 1996, Pages 1559-1563

  Gebauer, Olaf ^a   Brückner, Reinhard ^a  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

Author keywords

Chiral building blocks; Quinic acid; Regioselective acetalization; Regioselective protection

Indexed keywords

EID: 33749095113     PISSN: 09473440     EISSN: None     Source Type: Journal    
DOI: 10.1002/jlac.199619961010     Document Type: Article

References (18)

1. 4-impregnated silica gel whereupon preparative TLC provided (A)-4-hydroxy-2-cyclohexen-1-one in 41% yield.
2. (R)-4-Hydroxy-2-cyclohexen-1-one is obtainable from (9S)-9-methyl-1-phenylbicycio[4.3.0]nona-1,3-diene in 4 steps [(1) Diels-Alder reaction with benzoquinone at 6.5 kbar, (2) hydrogenation, (3) reduction with L-selectride®, and (4) thermolysis] and 35% overall yield according to R. Brünjes, U. Tilstam, E. Winterfeldt, Chem. Ber. 1991, 124, 1677-1678. (9S)-9-methyl-1-phenylbicyclo[4.3.0]nona-1,3-diene can be prepared from the "unnatural" Hajos-Wiechert ketone (7a.R)-2,3,7,7a-tetrahydro-7a-methyl-1H-indene-1,5(6H)-dione [preparable in 3 steps and 76% yield from 2-methyl-1,3-cyclopentanedione, methyl vinyl ketone, and cat.
3. (R)-proline as described for the enantiomeric series by Z. G. Hajos, D. R. Parrish, Org. Synth. Coll. Vol. 7, 1990, 363-368]
4. in 5 steps and 29% overall yield according to K. Matcheva, M. Beckmann, D. Schomburg, E. Winterfeldt, Synthesis 1989, 814-817.
5. T. Kamikubo, K. Hiroya, K. Ogasawara, Tetrahedron Lett. 1996, 37, 499-502 [key step: desymmetrization of a meso-configured tricyclic derivative of 3,6-bis(trimethylsiloxy)-1-cyclohexane by Rh(I)-BINAP-catalyzed double bond migration].
6. [3]: S. Takano, Y. Higashi, T. Kamikubo, M. Moriya, K. Ogasawara, Synthesis 1993, 948-950 (key step: desymmetrization of a meso-configured tricyclic derivative of 2-cyclohexene-1,4-diol by lipase-catalyzed monoacetylization).
7. 2 adducts of cis-3,6-diacetoxy-1-cyclohexene followed by sequential treatment with Zn and Collins' reagent give (S)-acetoxy-2-cyclohexen-1-one in 97% ee: R. J. Kazlauskas, A. N. E. Weissfloch, A. T. Rappoport, L. A. Cuccia, J. Org. Chem. 1991, 56, 2656-2665. However, using other enzymes under similar conditions no (R)-acetate was obtained.
8. [5b] The baker's yeast-mediated monoreduction of a diketone possessing the structure (but not origin) of a Diels-Alder adduct of 2-cyclohexene-1,4-dione and cyclopentadiene and a subsequent [4 + 2] cycloreversion gave (5)-4-hydroxy-2-cyclohexen-1-one (67% ee): A. P. Marchand, D. Xing, Y. Wang, S. G. Bott, Tetrahedron: Asymmetry 1995, 6, 2709-2714.
9. B. M. Trost, A. G. Romero, J. Org. Chem. 1986, 51, 2332-2342.
10. J. E. Audia, L. Boisvert, A. D. Patten, A. Villalobos, S. J. Danishefsky, J. Org. Chem. 1989, 54, 3738-3740.
11. 12 catalyzed in situ isomerization].
12. S. V. Ley, H. W. M. Priepke, S. L. Warriner, Angew. Chem. 1994, 106, 2410-2412;
13. Angew. Chem. Int. Ed. Engl. 1994, 33, 2288-2290;
14. S. V. Ley, H. W M. Priepke, Angew. Chem. 1994, 706, 2412-2414;
15. Angew. Chem. Int. Ed. Engl. 1994, 33, 2290-2292.
16. D = -25.3 (S-4a, 17% ee by GLC; c= 1.42 in MeOH).
17. W. C. Still, M. Kahn, A. Mitra, J. Org. Chem. 1978, 43, 2923-2925.
18. After submission of this manuscript Frost et al. reported on a bicyclic bisacetal analog of our compound 8; it was obtained from the methyl ester of quinic acid, 2,2,3,3-tetramethoxybutane, and trimethyl orthoformate in a transacetalization reaction very similar to ours: J.-L. Montchamp, F. Tian, M. E. Hart, J. W. Frost, J. Org. Chem. 1996, 61, 3897-3899.