Reaction Pathway and Stereoselectivity of Asymmetric Synthesis of Chrysanthemate with the Aratani C 1-Symmetric Salicylaldimine−Copper Catalyst

The reaction pathway and the mechanism of asymmetric induction in the synthesis of (+)-trans-(1R,3R)-chrysanthemic acid methyl ester from methyl diazoacetate and 2,5-dimethyl-2,4-hexadiene in the presence of a C 1-chiral salicylaldimine Cu(I) complex has been probed with the aid of hybrid density fu...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-06, Vol.126 (23), p.7271-7280
Main Authors: Suenobu, Katsuhiro, Itagaki, Makoto, Nakamura, Eiichi
Format: Article
Language:English
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Summary:The reaction pathway and the mechanism of asymmetric induction in the synthesis of (+)-trans-(1R,3R)-chrysanthemic acid methyl ester from methyl diazoacetate and 2,5-dimethyl-2,4-hexadiene in the presence of a C 1-chiral salicylaldimine Cu(I) complex has been probed with the aid of hybrid density functional calculations. The key finding is that the alkoxycarbonyl carbene complex intermediate is intrinsically chiral and that the intramolecular hydrogen bonding in the carbene complex transmits the chirality information from the side chain to the carbene complex. Molecular orbital backgrounds of the structure of the carbene complex and the transition state of the cyclopropanation have been elucidated.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja031524c