Abstract
Methyl 2-cyclopropyl-2-diazoacetate was synthesized from acetylcyclopropane in few chemical steps in ∼55% total yield. Its copper or rhodium-catalyzed dediazoniation exclusively proceeds through the intramolecular isomerization of generated cyclopropyl(methoxycarbonyl)carbene to 1-methoxycarbonylcyclobutene, irrespective of the presence or the absence of unsaturated compounds. However, in the presence of acrylates or strained cycloalkenes, this diazo ester is being slowly involved into the 1,3-dipolar cycloaddition, giving cyclopropyl-substituted pyrazolinecarboxylates, which in case of 1-pyrazolines easily lose nitrogen molecule to selectively afford 1-cyclopropylcyclopropanecarboxylate derivatives.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
M. Regitz and H. Heydt, 1,3-Dipolar Cycloaddition Chemistry, Ed. A. Padwa, Wiley Interscience, New York, 1984, v. 1, p. 393.
G. Maas, The Chemistry of Heterocyclic Compounds, Eds A. Padwa and W. H. Pearson, J. Wiley & Sons, Inc., 2002, v. 59, p. 539.
O. M. Nefedov, E. A. Shapiro, and A. B. Dyatkin, Diazoacetic Acids and Derivatives, Ed. Patai Saul, Wiley, Chichester, UK, 1992, 2 (Pt. 2), 1475–1637.
G. Maas, Top. Curr. Chem., 1987, 137, 75.
M. P. Doyle, M. A. McKervey, and T. Ye, Modern Catalytic Methods for Organic Synthesis with Diazo Compounds; Wiley, New York, 1998, 652 pp.; (b) Ibid. p. 238.
M. B. Sohn and M. Jones, Jr., J. Am. Chem. Soc., 1972, 94, 8280.
R. R. Gallucci and M. Jones, Jr., J. Am. Chem. Soc., 1976, 98, 7704.
M. B. Sohn, M. Jones, Jr., M. E. Hendrick, R. R. Rando, and W. von E. Doering, Tetrahedron Lett., 1972, 53.
I. Bašnák and J. Farkaš, Coll. Czechoslov. Chem. Commun., 1975, 40, 1038.
A. M. Guliev, G. A. Ramazanov, S. S. Gasanova, and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim., 1984, 2729 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1984, 33, 2498 (Engl. Transl.)].
W. von der Saal, R. Reinhardt, H.-M. Seidenspinner, J. Stawitz, and H. Quast, Lieb. Ann. Chem., 1989, 703.
D. H. White, P. B. Condit, and R. G. Bergman, J. Am. Chem. Soc., 1972, 94, 1348.
M.-A. Plancquaert, Ph. François, R. Merényi, and H. G. Viehe, Tetrahedron Lett., 1991, 32, 7265.
A. P. Meshcheryakov and V. G. Glukhovtsev, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 1959, 1490 [Bull. Acad. Sci USSR, Div. Chem. Sci., 1959, 7 (Engl. Transl.)].
R. J. Griffin, C. E. Arris, C. Bleasdale, F. T. Boyle, A. H. Calvert, N. J. Curtin, C. Dalby, S. Kanagula, N. K. Lembicz, D. R. Newell, A. E. Pegg, and B. T. Golding, J. Med. Chem., 2000, 43, 4071.
Author information
Authors and Affiliations
Corresponding author
Additional information
Dedicated to Academician V. A. Tartakovsky in honor of his 75th anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1459–1465, August, 2007.
Rights and permissions
About this article
Cite this article
Prokopenko, V.V., Okonnishnikova, G.P., Klimenko, I.P. et al. Synthesis and chemical transformations of 2-cyclopropyl-2-diazoacetates. Russ Chem Bull 56, 1515–1521 (2007). https://doi.org/10.1007/s11172-007-0234-6
Received:
Issue Date:
DOI: https://doi.org/10.1007/s11172-007-0234-6