Expanding the Scope of Chelating Triazolylidenes: Mesoionic Carbenes from the 1, 5‐"Click"‐Regioisomer and Catalytic Synthesis of Secondary Amines from Nitroarenes. Issue 50 (4th November 2016)

• Record Type: Journal Article
• Authors: Suntrup, Lisa; Hohloch, Stephan; Sarkar, Biprajit
• Is Part Of: Chemistry. Volume 22:Issue 50(2016)
• Page Start: 18009
• Page End: 18018
• Publication Date: 2016-11-04
• Subjects: regioselectivity -- carbene ligands -- carbenes -- click chemistry -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201603901
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Chelating 1, 2, 3‐triazolylidenes have been established as privileged ligands in homogeneous catalysis. We present herein a new approach towards chelating 1, 2, 3‐triazolylidene ligands based on the 1, 5‐regioisomer of the corresponding triazole, which can be obtained through simple click chemistry. The new ligands are compared to their 1, 4‐regioisomeric counterparts through coordination to the ruthenium p ‐cymene fragment. The complexes are characterized structurally and spectroscopically and are employed as (pre)catalysts in the reductive condensation of nitroarenes and primary alcohols to yield secondary amines. The activity of chelating mesoionic carbene ligands obtained from the two different regioisomers of the triazoles are compared and contrasted in catalysis. The performance of the ruthenium complexes with mesoionic carbenes could be improved through the choice of the employed base and reaction conditions, giving rise to the most effective systems thus far. The results presented here prove the utility of chelating mesoionic carbenes as an extremely potent class of ligands for the synthesis of secondary amines from nitroarenes. Abstract : Ru getting into gear : The use of the 1, 5‐regiomer of the azide–alkyne cycloaddition reaction for the development of chelating mesoionic carbene ligands is reported (see scheme). The corresponding ruthenium complexes are shown to be extremely potent catalysts for the synthesis of secondary amines.