Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed N-Alkylation of Amines.

IF 4.2 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY Molecules Pub Date : 2025-02-18 DOI:10.3390/molecules30040951

Neslihan Şahin, Christophe Gourlaouen, David Sémeril

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Abstract

Two bis-ruthenium(II) complexes, namely N,N'-{5,17-diamino-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}-bis-[dichloro-(p-cymene)-ruthenium(II)] (1) and N,N'-{5,11-diamino-4(24),6(10),12(16), 18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}-bis-[dichloro-(p-cymene)-ruthenium(II)] (2) were synthesized and tested as catalysts in the N-alkylation of primary amines with arylmethyl alcohol using the green "hydrogen borrowing" methodology. The catalytic results were compared with those obtained when the N-{5-amino-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentyl-resorcin[4]arene}-[dichloro-(p-cymene)-ruthenium(II)] (3) complex was employed as catalyst. The rate of the N-alkylation of aniline with benzyl alcohol increased in the order 3 < 1 ≪ 2, which highlights the importance of the relative positioning of the two metal centers on the upper rim of the resorcin[4]arene. Theoretical investigations suggest that the grafting of the two "RuCl₂(p-cymene)NH₂" moieties on two distal aromatic rings of the cavitand allows a cooperative effect between a ruthenium atom and the coordinated amine of the second metal center.

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来源期刊

Molecules 化学-有机化学

CiteScore

7.40

自引率

8.70%

发文量

7524

审稿时长

1.4 months

期刊介绍： Molecules (ISSN 1420-3049, CODEN: MOLEFW) is an open access journal of synthetic organic chemistry and natural product chemistry. All articles are peer-reviewed and published continously upon acceptance. Molecules is published by MDPI, Basel, Switzerland. Our aim is to encourage chemists to publish as much as possible their experimental detail, particularly synthetic procedures and characterization information. There is no restriction on the length of the experimental section. In addition, availability of compound samples is published and considered as important information. Authors are encouraged to register or deposit their chemical samples through the non-profit international organization Molecular Diversity Preservation International (MDPI). Molecules has been launched in 1996 to preserve and exploit molecular diversity of both, chemical information and chemical substances.