Enantiocontrol in intramolecular cyclopropanation of diazoketones. Conformational control of metal carbene alignment |
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| Authors: | M P Doyle M Yu Eismont Q L Zhou |
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| Institution: | (1) Trinity University, 78212 San Antonio, Texas, USA;(2) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp, 117913 Moscow, Russian Federation;(3) Institute of Fine Chemicals, East China University of Science and Technology, 130 Meilong Lu, 200237 Shanghai, Peoples Republic of China |
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| 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.
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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| Keywords: | diazo ketones enantioselective intramolecular cyclopropanation chiral dirhodium(ii) carboxamidates chiral copper semicorrins chiral copper bisoxazolines metal carbenes |
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