Preparation and reactions of magnesiated uracil derivatives

Synlett

Volumn , Issue 10, 1999, Pages 1577-1578

  Abarbri, Mohamed ^a   Knochel, Paul ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

Copper; Functionalized organometallics; Magnesium; Uracil

Indexed keywords

REAGENT; URACIL DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE;

EID: 0032825750     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2891     Document Type: Article

References (19)

1. a) Newkome, G. R.; Pandler, W. W. Contemporary Heterocyclic Chemistry, Wiley, New York, 1982;
2. b) Gilchrist, T. L. Heterocyclen-Chemie, VCH, Weinheim, 1995.
3. a) Snieckus, V. Chem. Rev. 1990, 90, 879,
4. b) Rocca, P.; Marsais, F.; Godard, A.; Quéguinet, G. Tetrahedron 1993, 49, 49,
5. Sakamoto, T.; Kondo, Y.; Murata, N.; Yamanaka, H. Tetrahedron 1993, 49, 9713.
6. a) Stevenson, T. M.; Prasad, A. S. B.; Citineni, J. R.; Knochel, P. Tetrahedron Lett. 1996, 37, 8375,
7. b) Prasad, A S. B.; Stevenson, T.M.; Citineni, J. R.; Nyzam, V.; Knochel, P. Tetrahedron 1997, 53, 7237,
8. d) Bérillon, L.; Wagner, R.; Knochel, P. J. Org. Chem. 1998, 63, 9117,
9. e) Prasad, A. S. B.; Knochel, P. Tetrahedron 1997, 53, 16711.
10. Boymond, L.; Rottländer, M.; Cahiez, G.; Knochel, P. Angew. Chem. Int. Ed. Engl. 1998, 37, 1701.
11. Rottländer, M.; Boymond, L.; Cahiez, G.; Knochel, P. J. Org. Chem. 1999, 64, 1080.
12. Bérillon, L.; Leprêtre, A.; Turck, A.; Plé, N.; Quéguiner, G.; Cahiez, G.; Knochel, P. Synlett 1998, 1359.
13. Commercially available 5-iodouracil was protected according to: Das, B.; Kundu, N. G. Synth. Commun. 1998, 18, 855.
14. The preparation and reaction of immonium salts with functionalized organozinc and magnesium derivatives will be reported separately: Millot, N.; Avolio, S.; Piazza, C. and Knochel, P. manuscript in preparation.
15. a) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117,
16. b) Knochel, P. Synlett 1995, 393,
17. c) Knochel, P.; Perea, J. J. A.; Jones, P. Tetrahedron 1998, 54, 8275.
18. Villieras, J.; Rambaud, M. Synthesis 1982, 924.
19. Typical procedure: Preparation of 5-(2-carbethoxy-2-propenyl) N, N-dibenzyluracil (3k; entry 11 of Table I). A dry three necked flask equipped with a magnetic stirring bar, a thermometer and a septum was charged with 5-iodo-N,N-dibenzyluracil (1a; 1.3 g, 3.1 mmol) in THF (3 mL) and cooled to -40 °C. i-PrMgBr (3.4 mL, 3.4 mmol, 1M in THF) was dropwise added and the reaction mixture was stirred at -40 °C for 45 min. CuCN (28 mg, 0.3 mmol) was added followed by ethyl (2-bromomethyl)acrylate (675 mg, 3.5 mmol). The reaction mixture was stirred 1h at -40°C, then allowed to warm to 0 °C and worked up as usual. The crude residue obtained after evaporation of the solvents was purified by flash-chromatography (pentane: ether = 6 : 4) yielding the pure product 3k (954 mg, 76 % yield) as a colorless oil.