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

Cristina Cimarelli; Corrado Bacchiocchi; Manuel Petroselli; Martina Lippolis; Dario Gentili; Serena Gabrielli

doi:10.1055/a-1990-4867

Synthesis, Inhaltsverzeichnis

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 ∗

^aSchool of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy

,

Corrado Bacchiocchi ∗

^aSchool of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy

,

Manuel Petroselli ∗

^bLaboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, Zürich 8093, Switzerland

,

Martina Lippolis

^aSchool of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy

,

Dario Gentili

^aSchool of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy

,

Serena Gabrielli

^aSchool of Science and Technology, Chemistry Division, University of Camerino, ChIP building, Via Madonna delle Carceri, 62032 Camerino, Italy

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Abstract

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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

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