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Theoretical investigation of direct amination of β-ketoesters catalyzed by copper(II)-bisoxazoline(BOX)

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Abstract

The mechanism of the direct amination of β-keto esters catalyzed by copper(II)-bisoxazoline has been studied by means of density functional theory of B3LYP method. The computational results support the present mechanism, which involves (i) the generation of the enol from β-keto esters, which coordinates to copper(II)-bisoxazoline. The coordination step appears to be fast, exothermic, and irreversible. (ii) The formation of the σ(N-C) bond via a six-membered ring transition state after azo dicarboxylate coordination with the chiral catalyst. This step is chirality-control step. (iii) Intramolecular hydrogen migration generates a catalyst-product complex, which can finally yield product. The hydrogen shift is the rate-determining step, which affords the experimentally observed (R)-product. The stereochemical predictions have been rationalized in terms of steric repulsions, showing good agreement with experimental data.

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Authors and Affiliations

  1. Department of Chemistry, Southwest University, Chongqing, 400715, People’s Republic of China

    Youqing Yu, Wei Shen, Jinsheng Zhang, Rongxing He & Ming Li

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  1. Youqing Yu
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  2. Wei Shen
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  3. Jinsheng Zhang
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  4. Rongxing He
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  5. Ming Li
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Correspondence to Ming Li.

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Yu, Y., Shen, W., Zhang, J. et al. Theoretical investigation of direct amination of β-ketoesters catalyzed by copper(II)-bisoxazoline(BOX). J Mol Model 14, 237–247 (2008). https://doi.org/10.1007/s00894-007-0266-8

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  • DOI: https://doi.org/10.1007/s00894-007-0266-8

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