Heterocyclic thiolates and phosphine ligands in copper‐catalyzed synthesis of propargylamines in water. (2nd March 2021)

• Record Type: Journal Article
• Authors: Neshat, Abdollah; Gholinejad, Mohammad; Afrasi, Mahmoud; Mastrorilli, Piero; Todisco, Stefano; Gilanchi, Shirin; Osanlou, Farzane
• Is Part Of: Applied organometallic chemistry. Volume 35:Number 5(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-03-02
• Subjects: 2‐mercaptobenzothiazole -- A3 coupling -- catalysis -- methimazole -- propargylamines; Organometallic chemistry -- Periodicals; Organometallic compounds -- Periodicals; 547.05
• DOI: 10.1002/aoc.6180
• Languages: English
• ISSNs: 0268-2605

Abstract

Abstract : The product obtained by reaction of deprotonation of 2‐mercaptobenzothiazole or methimazole (2‐mercapto‐1‐methylimidazole) with copper iodide in the presence of tertiary phosphines, PR2 R' (R = R' = cyclohexyl; R = R' = phenyl; R = phenyl, R' = methyl) showed high catalytic activity in A 3 coupling of a series of aldehydes with phenylacetylene and piperidine, yielding propargylamines. An investigation into the nature of active species carried out mainly by electrospray ionization mass spectrometry (ESI‐MS) techniques underscores a crucial role played by organosulfur and organophosphorus compounds in the generation of active species responsible for these reactions. The coupling reactions were successfully carried out at low catalyst loadings in water/THF (20:1) and in relatively short reaction times. The scope of the reaction was also investigated with 20 examples. Abstract : Cu(II) and Cu(I) complexes with organosulfur and organophosphorus ligands were synthesized and characterized by ESI‐MS techniques. The catalytic activity of the copper complexes was investigated in A 3 coupling reactions under low catalyst loadings at room temperature. Among these Cu complexes, a heteroleptic copper complex with the 2‐mercaptobenzothialoe and triphenylphosphine ligands showed highest activity in catalytic reactions.