Reaction of diazoalkanes with unsaturated compounds. 9 Catalyzed cyclomethylenation of trimethylsilylacetylenes by diazomethane
- 59 Downloads
The catalyzed reaction of methyl-, propyl-, and cyclopropyltrimethylsilylacetylenes with diazomethane in the presence of CuCl leads to the corresponding cyclopropenes and bicyclobutanes with overall yields of up to 70%, and also to the products of incorporation of a methylene group into the C3-H bond of the cyclopropenes formed (2–9%). Partial catalyzed isomerization of the 1-trimethylsilyl-2-cyclopropylcyclopropene formed from trimethylsilylcyclopropylacetylene, into 1-trimethylsilyl-1-cyclopropylallene (yield ∼50%) was discovered to proceed under the reaction conditions.
KeywordsMethyl CuCl Propyl Cyclopropenes Diazomethane
Unable to display preview. Download preview PDF.
- 1.Yu. V. Tomilov, A. B. Kostitsyn, V. A. Dokichev, et al., Izv. Akad. Nauk SSSR, Ser. Khim. No. 12, 2752 (1989).Google Scholar
- 2.Yu. V. Tomilov, A. B. Kostitsyn, and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim. No. 9, 2156 (1989).Google Scholar
- 3.G. Maas, Topics in Current Chemistry,137, 170 (1987).Google Scholar
- 4.W. von E. Doering and J. E. Coburn, Tetrahedron Lett., No. 15, 991 (1965).Google Scholar
- 5.M. Regitz and H. Heydt, 1,3-Dipolar Cycloaddition Chemistry, Vol. 1, Wiley Interscience, New York (1984), 433, 502.Google Scholar
- 6.A. T. Stell and E. Negishi, Tetrahedron Lett.,46, 5671 (1985).Google Scholar
- 7.I. E. Dolgii, G. P. Okonnishnikova, and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim., No. 4, 822 (1979).Google Scholar