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

IF 4.6 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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钌催化胺n -烷基化反应中金属中心位置对空腔的影响。

合成了N，N'-{5,17-二氨基-4（24）、6（10）、12（16）、18（22)-四亚基二氧基-2,8,14,20-四四烯基间苯二烯-2 -[二氯-（对）花氧基）-钌（II）](1)和N，N'-{5,11-二氨基-4（24）、6（10）、12（16）、18（22)-四亚基二氧基-2,8,14,20-四烯基间苯二烯-2 -[二氯-（对）花氧基）-钌（II）](2)两种双钌（II）配合物，并采用绿色“借氢”法测试了它们作为伯胺与芳基甲醇N-烷基化反应的催化剂。并与N-{5-氨基-4(24),6(10),12(16),18(22)-四亚甲基二氧基-2,8,14,20-四戊基-间苯二酚芳烃}-[二氯-（对伞花烃）-钌（II）](3)配合物作催化剂的催化效果进行了比较。苯胺与苯甲醇的n -烷基化率以3 < 1 < 2的顺序增加，这突出了在间苯芳烃上边缘的两个金属中心的相对位置的重要性。理论研究表明，两个“RuCl2（对伞花烃）NH2”基团接枝在腔体的两个远端芳香环上，使得钌原子与第二个金属中心的配位胺之间发生协同作用。

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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.