Enzymatic resolution of amines and amino alcohols using pent-4-enoyl derivatives

Tetrahedron Letters

Volumn 37, Issue 35, 1996, Pages 6287-6290

  Takayama, Shuichi ^a   Moree, Wilna J ^a   Wong, Chi Huey ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; AMINOALCOHOL;

ARTICLE; DERIVATIZATION; DRUG PURIFICATION; ENANTIOMER; TECHNIQUE;

EID: 0030603054     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01378-0     Document Type: Article

References (18)

1. 1. (a) Schoffers, E.; Golebiowski, A.; Johnson, C. R. Tetrahedron 1996, 52, 3769.
2. (b) Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry; Pergamon: Oxford, 1994 and references cited therein.
3. 2. (a) Orsat, B.; Alper, P. B.; Moree, W. J.; Mak, C-P.; Wong, C.-H. J. Am. Chem. Soc. 1996, 118, 712.
4. (b) Pozo, M.; Gotor, V. Tetrahedron 1993, 49, 10725.
5. (c) Gotor, V.; Menéndez, E.; Mouloungui, Z.; Gasset, A. J. Chem. Soc., Chem. Commun. 1993, 2453.
6. (d) Pozo, M.; Pulido, R.; Gotor, V. Tetrahedron 1992, 48, 6477.
7. (e) Fernández, S.; Brieva, R.; Rebolledo, F.; Gotor, V. J. Chem. Soc., Chem. Commun. 1992, 2885.
8. (f) Kitaguchi, H.; Fitspatrick, P. A.; Huber, J. E.; Klibanov, A. M. J. Am. Chem. Soc. 1989, 111, 3094.
9. 3. Madsen, R.; Roberts, C.; Fraser-Reid, B. J. Org. Chem. 1995, 60, 7920.
10. 4. Wang, Y.-F.; Lalonde, J. J.; Momongan, M.; Bergbreiter, D. E.; Wong, C.-H. J. Am. Chem. Soc. 1988, 110, 7200.
11. 4, and concentrated in vacuo. The residue was distilled (bp 96°C/4 mmHg) to give the title compound (6.5 g, 94%). For other example of cyanomethyl ester synthesis, see: West, J. B.; Hennen, W. J.; Lalonde, J. L.; Bibbs, J. A.; Zhong, Z.; Meyer, E. F. J.; Wong, C.-H. J. Am. Chem. Soc. 1990, 112, 5313.
12. 6. Morís, F.; Gotor, V. Tetrahedron, 1992, 48, 9869.
13. 3, c= 0.22) obtained chemically from authentic (R)-amine (98% ee).
14. 4 and concentrated in vacuo to give an oil. Much of the pent-4-enamide alcohol (8.5 mg) was crystallized out at this stage by addition of diisopropyl ether. The mother liquor was chromatographed (SiO2, hexane/EtOAc, 9/1-1/1) to give the dipent-4-enoyl product (13 mg, 27%) and some more of the pent-4-enamide alcohol (total 17 mg, 50 %). The enantiomeric excess of the dipent-4-enoyl product was determined to be 83% ee by HPLC analysis (CHIRALPAK AD, hexane/IPA 95/5, v/v, 1.0 ml/min).
15. 9. With diallyl carbonate the highest ee observed was 40% (15% yield). At higher pH, N-acylation was quantitative but the ee was 0% due to spontaneous non-enzymatic reaction. Acylation of alcohols were not observed when diallyl carbonate was the acyl donor.
16. 3N to lipase reactions, see: Theil, F.; Ballschuh, S.; Schick, H.; Haupt, M.; Hafner, B.; Schwarz, S. Synthesis 1988, 540.
17. 4 and concentrated in vacuo. Addition of diisopropyl ether and crystallization afforded 94 mg of the hydrolyzed product. The mother liquor was chromatographed to afford the unhydrolyzed dipent-4-enoyl compound (154 mg, 50%) and another 29 mg of pent-4-enamide alcohol (total 113 mg, 50%). The enantiomeric excess of the unhydrolyzed dipent-4-enoyl compound was determined to be 91% ee by HPLC analysis (CHIRALPAK AD, hexane/IPA 95/5, v/v, 1 ml/min).
18. 12. For a similar example, see: van Boom, J. H.; Burgers, P. M. J. Tetrahedron Lett. 1976, 17, 4875.