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Synthesis 2023; 55(08): 1241-1252
DOI: 10.1055/a-1990-4867
paper

Diastereoselective Synthesis of Secondary Propargylamines Exploiting CuI-Based Promoters and Determination of Their Relative Configuration by DFT-GIAO Conformational Analysis

Cristina Cimarelli  ∗
a   School of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy
,
Corrado Bacchiocchi  ∗
a   School of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy
,
Manuel Petroselli  ∗
b   Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, Zürich 8093, Switzerland
,
Martina Lippolis 
a   School of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy
,
Dario Gentili
a   School of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy
,
Serena Gabrielli 
a   School of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy
› Author AffiliationsThe work was financially supported by the University of Camerino under the framework of the University Research Project ‘FAR2018: Fondo di Ateneo per la Ricerca’. The authors are thankful to Fratelli Guzzini Recanati for granting a doctoral fellowship to M.L.
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Abstract

The stereoselective synthesis of several secondary propargylamines by the copper-promoted A3-coupling reaction of aliphatic and aromatic aldehydes with phenylacetylene and (R)-(+)-phenylethylamine is here reported. Two different synthetic methodologies have been investigated in this study, involving CuSO4/NaI and ­CeCl3·7H2O/CuI promoting systems. The reported methodologies were compared in terms of efficiency, diastereoselectivity, and toxicity, both showing advantages with respect to the current methodologies. The relative configurations of each of the obtained propargylamines, previously unknown in the literature, were assigned by comparison of the 1H NMR experimental chemical shifts with those theoretically predicted via the DFT-GIAO method.

Key words

propargylamines - A3 coupling - relative configuration - copper promoter - DFT calculations - stereoselective synthesis - diastereoselectivity

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1990-4867. The computational data sets generated for this study are available upon reasonable request to the corresponding author.
  • Supporting Information


Publication History

Received: 12 October 2022

Accepted after revision: 30 November 2022

Accepted Manuscript online:
30 November 2022

Article published online:
20 January 2023

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