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Stereochemical outcome of copper-catalyzed C-H insertion reactions. An experimental and theoretical study. 2013

Gonzalo Jiménez-Osés, and Eugenio Vispe, and Marta Roldán, and Sergio Rodríguez-Rodríguez, and Pilar López-Ram-de-Viu, and Luis Salvatella, and José A Mayoral, and José M Fraile
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United States. gjimenez@chem.ucla.edu

The combination of chiral preparative HPLC separation, VCD measurements, and theoretical calculations allows the unambiguous determination of the absolute configuration of the conformationally flexible products of copper-catalyzed carbene insertion reactions. DFT calculations were used to predict the stereochemical outcome of the copper-bis(oxazoline)-catalyzed C-H insertion reaction between methyl diazophenylacetate and tetrahydrofuran and also to predict the absolute configuration of the major stereoisomers derived from the same reaction with different cyclic ethers. These predictions were verified experimentally through NMR and VCD spectroscopy and allowed rationalization of the stereochemical outcome of these reactions without further derivatization of the products, which can be prblematic under certain conditions as described herein.

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