Dimethylation and hydrodechlorination of gem-dichlorocyclopropanes with grignard reagents promoted by Fe(III) or Co(II) catalyst

Synlett

Volumn , Issue 1, 1998, Pages 67-69

  Nishii, Yoshinori ^a   Wakasugi, Kazunori ^a   Tanabe, Yoo ^a  

^a KWANSEI GAKUIN UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002718402     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1998-1581     Document Type: Article

References (39)

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22. 3FeLi with gem-dibromocyclopropanes was reported: Corey, E. J.; Posner, G. H. Tetrahedron Lett. 1970, 315.
23. 3 catalyst, complex mixtures of 1-bromo-1-methyl-2-phenylcyclopropane, 1-bromo-2-phenylcyclopropane, and phenylcyclopropane except the desired product were produced.
24. The controlled reaction of 1a with an equimolar amount of MeMgBr gave 31% of dimethylated product 2a with 60% recovery of 1a (GLC conversion).
25. 2 were not effective.
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29. Molander, G. A.; Rahn, J. B.; Shubert, D. C.; Bonde, S. E. Tetrahedron Lett. 1983, 24, 5449. The role of 4-methoxytoluene or p-xylene may be an effective mediator of the redox system from Fe (III) to Fe (I). These electron-rich benzenes are known to form CT complexes with Fe (III) salts.
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31. 3 are reported. Kauffmann, T. Angew. Chem. Int. Ed. Engl. 1996, 35, 386.
32. 1H NMR (400 MHz) δ 0.25-0.35 (2H, m), 0.92 (3H, s), 1.01 (3H, s), 1.23-1.79 (12H, m).
33. 2 (5%).
34. 4-Methoxytoluene or p-xylene did not accelerate this hydrodechlorination, which might proceed through another mode of the dimethylation.
35. 2 (19%).
36. 1H NMR (400 MHz) δ 0.79-1.18 (3H, m), 1.19-1.75 (9H, m), 1.81 (2H x 7/12, m), 2.13 (2H x 5/12, m), 2.42 (1H x 5/12, dd, J = 3.2 Hz, J = 3.4 Hz), 3.25 (1H x 7/12, dd, J = 7.3 Hz, J = 7.6 Hz).
37. 4 (0.1 equiv), 1 h, 48%. Ti-mediated method using 1i failed to afford the desired product but gave the corresponding diethylated alcohol (-50%).
38. Nishii, Y.; Matsumura, H.; Muroya, Y.; Tsuchiya, T.; Tanabe, Y. Biosci. Biotech. Biochem, 1995, 59, 1355.
39. Nishii, Y.; Wakimura, K.; Tsuchiya, T.; Nakamura, S.; Tanabe, Y. J. Chem. Soc., Perkin Trans. 1 1996, 1243.