Conjugate addition of RMgX-3MeLi to α,β-unsaturated amides and α,β-unsaturated carboxylic acids

Chemistry Letters

Volumn 36, Issue 6, 2007, Pages 736-737

  Kikuchi, Mikiko ^a   Niikura, Satomi ^a   Chiba, Nao ^a   Terauchi, Nahoko ^a   Asaoka, Mono ^a  

^a JAPAN WOMEN'S UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 34347207139     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2007.736     Document Type: Article

References (21)

1. T. Hinago, N. Teshima, S. Kenmoku, T. Kamata, N. Terauchi, N. Chiba, C. Satoh, A. Nakamura, M. Asaoka, Chem. Lett. 2007, 36, 54.
2. Similar behavior of MeLi has already been reported: M. J. Aurell, R. Mestres, E. Munoz, Tetrahedron Lett. 1998, 39, 6351.
3. V. J. Lee, in Comprehensive Organic Synthesis, ed. by B. M. Trost, I. Fleming, Pergamon, Oxford, 1991, Vol. 4, p. 74.
4. G. B. Mpango, K. K. Mahalanabis, Z. Mahadavi-Damghani, V. Snieckus, Tetrahedron Lett. 1980, 21, 4823.
5. 3, gave 1,4-adducts by the reactions with crotonic acid and tiglic acid: Y. Yamamoto, Angew. Chem., Int. Ed. Engl. 1986, 25, 947;
6. Y. Yamamoto, S. Yamamoto, H. Yatagai, Y. Ishihara, K. Maruyama, J. Org. Chem. 1982, 47, 119;
7. Y. Yamamoto, K. Maruyama, J. Am. Chem. Soc. 1978, 100, 3240.
8. Under harsh reaction conditions, Grignard reagents react with some α,β-unsaturated carboxylic acids to give low yields of adducts: J. H. Wotiz, J. S. Matthews, H. Greenfield, J. Am. Chem. Soc. 1953, 75, 6342;
9. J. Klein, Tetrahedron 1964, 20, 465;
10. J. Klein, N. Aminadav, J. Chem. Soc. C 1970, 1380;
11. J. Klein, S. Zitrin, J. Org. Chem. 1970, 35, 666.
12. 4Cl (2 mL), extraction with ethyl acetate, and purification by silica gel TLC (hexane:AcOEt =1:1) gave 2a in 82% yield as a colorless oil.
13. 2Mg
14. 10
15. 2MgLi to carbonyl compounds, see: H. Hatano, T. Matsumura, K. Ishihara, Org. Lett. 2005, 7, 573;
16. For the chemistry of RaMgLi, see: S. Dumouchel, F. Mongin, F. Trecourt, G. Queguinter, Tetrahedron Lett. 2003, 44, 2033;
17. A. Inoue, J. Kondo, H. Shinokubo, K. Oshima, Chem. Eur. J. 2002, 8, 1730;
18. A. Inoue, K. Kitagawa, H. Shinokubo, K. Oshima, J. Org. Chem. 2001, 66, 4333, and references therein.
19. L. M. Seitz, T. L. Brown, J. Am. Chem. Soc. 1966, 88, 4140;
20. H. O. House, R. A. Latham, G. M. Whitesides, J. Org. Chem. 1967, 32, 2481.
21. 2O, 2.7mL, 3 mmol) at 0°C. After stirring for 30 min at that temperature, the mixture was cooled to -30 °C. 5-Phenyl-2-pentenoic acid (45 mg, 0.25 mmol) in THF (4 mL) was added and the reaction mixture was stirred under Ar at -30 °C for 1.5 h. Quenching with 2 M HCl (4mL), extraction with ethyl acetate, and concentration gave a crude oil which was treated with N,Ndimethylformamide dimethyl acetal (300 μL) at 80 °C for 2h. Condensation and purification by silica gel TLC (hexane:AcOEt = 10:1) gave methyl 3-t-butyl-5-phenyl-2pentenoate in 67% yield as a colorless oil.