Abstract
Diazo ketones with γ or δ double bonds undergo catalytic intramolecular cyclopropanation. These reactions occur with high enantiocontrol when catalyzed by copper semicorrins and bis-oxazolines, but low enantiocontrol characterizes reactions catalyzed by a broad selection of chiral dirhodium(ii) carboxamidates. The reverse stereocontrol occurs for intramolecular cyclopropanation of allylic and homoallytic diazoacetates and diazoacetamides. This divergence is explained by conformational control of carbonyl alignment (syn oranti to the metal) of the metal carbene intermediate.
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M. P. Doyle, W. R. Winchester, J. A. A. Hoorn, V. Lynch, S. H. Simonsen, and R. Ghosh,J. Am. Chem. Soc, 1993,115, 9968.
M. P. Doyle, R. E. Austin, A. S. Bailey, M. P. Dwyer, A. B. Dyatkin, A. V. Kalinin, M. M. Y. Kwan, S. Liras, C. J. Oalmann, R. J. Pieters, M. N. Protopopova, C. E. Raab, G. H. P. Roos, Q.-L. Zhou, and S. F. Martin,J. Am. Chem. Soc., 1995,117, 5763.
M. P. Doyle, W. R. Winchester, M. N. Protopopova, A. P. Kazala, and L. J. Westrum,Org. Synth., 1996,73, 13.
M. P. Doyle, M. Y. Eismont, M. N. Protopopova, and M. M. Y. Kwan,Tetrahedron, 1994,50, 1665.
M. P. Doyle, and A. V. Kalinin,J. Org. Chem., 1996,61, 2179.
M. P. Doyle,Izv. Akad. Nauk. Ser. Khim., 1994, 1879 [Russ. Chem. Bull., 1994,43, 1770 (Engl. Transl.)].
M. P. Doyle, Q.-L. Zhou, A. B. Dyatkin, and D. A. Ruppar,Tetrahedron Lett., 1995,36, 7579.
M. P. Doyle, W. R. Winchester, S. H. Simonsen and R. Ghosh,Inorg. Chim. Acta, 1994,220, 193.
M. P. Doyle, W. R. Winchester, M. N. Protopopova, P. Müller, G. Bernardinelli, D. Ene, and S. Motallebi,Helv. Chim. Acta, 1993,76, 2227.
M. P. Doyle, A. B. Dyatkin, M. N. Protopopova, C. I. Yang, C. S. Miertschin, and W. R. Winchester,Recl. Trav. Chem. Pays-Bas, 1995,114, 163.
M. P. Doyle, Q.-L. Zhou, C. E. Raab, G. H. P. Roos, S. H. Simonsen, and V. Lynch,Inorg. Chem., 1996,35, 6064.
C. Piqué, B. Fähndrich, and A. Pfaltz,Synlett, 1995, 491.
W. G. Dauben, R. T. Hendricks, M. J. Luzzio, and H. P. Ng,Tetrahedron Lett., 1990,31, 6969.
R. Tokunoh, H. Tomiyama, M. Sodeoka, and M. Shibasaki,Tetrahedron Lett., 1996,37, 2449.
E. Wenkert, L. L. Davis, L. Mylari, M. F. Solomon, R. da Silva, S. Shulman, R. J. Warnet, P. Ceccherelli, M. Curini, and R. Pelicciari,J. Org. Chem., 1982,47, 3242; (b) P. Wang and J. Adams,J. Am. Chem. Soc., 1994,116, 3296; (c) H. R. Sonawane, N. S. Bellur, J. R. Ahiya, and D. G. Kulkarni,J. Org. Chem., 1991,56, 1434.
M. P. Doyle and A. B. Kalinin,Izv. Akad. Nauk., Ser. Khim., 1995, 1798 [Russ. Chem. Bull., 1995,44, 1729 (Engl. Transl.)].
M. Regitz and G. Maas,Diazo Compounds, Academic Press, New York, 1986.
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Dedicated to Academician of the RAS O. M. Nefedov (on his 65th birthday).
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 995–998, May, 1997.
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Doyle, M.P., Eismont, M.Y. & Zhou, Q.L. Enantiocontrol in intramolecular cyclopropanation of diazoketones. Conformational control of metal carbene alignment. Russ Chem Bull 46, 955–958 (1997). https://doi.org/10.1007/BF02496127
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DOI: https://doi.org/10.1007/BF02496127