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

  1. Jiménez-Osés, G. 1
  2. Vispe, Eugenio . 2
  3. Roldán, M. 2
  4. Rodríguez-Rodríguez, Sergio. 2
  5. López-Ram-De-Viu, P. 2
  6. Salvatella, L. 2
  7. Mayoral, J.A. 2
  8. Fraile, J.M. 2
  1. 1 University of California Los Angeles
    info

    University of California Los Angeles

    Los Ángeles, Estados Unidos

    ROR https://ror.org/046rm7j60

  2. 2 Instituto de Síntesis Química y Catálisis Homogénea
    info

    Instituto de Síntesis Química y Catálisis Homogénea

    Zaragoza, España

    ROR https://ror.org/002smyt64

Journal:
Journal of Organic Chemistry

ISSN: 0022-3263

Year of publication: 2013

Volume: 78

Issue: 12

Pages: 5851-5857

Type: Article

DOI: 10.1021/JO400415B SCOPUS: 2-s2.0-84879404413 WoS: WOS:000320979500004 GOOGLE SCHOLAR

More publications in: Journal of Organic Chemistry

Abstract

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. © 2013 American Chemical Society.