An efficient protocol for the synthesis of thioethers via iron-catalyzed cross-coupling reaction and its mechanistic investigation. (15th January 2019)

• Record Type: Journal Article
• Authors: Sindhu, K.S.; Abi, T.G.; Mathai, George; Anilkumar, Gopinathan
• Is Part Of: Polyhedron. Volume 158(2019)
• Page Start: 270
• Page End: 276
• Publication Date: 2019-01-15
• Subjects: Cross coupling -- DFT -- Iron Catalyzed; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2018.11.004
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Experimental and mechanistic exploration of Fe‐catalyzed thioetherification of aryl halides with aryl thiols using non-toxic and universal ligandl -proline. Abstract: One of the most straightforward methods for the synthesis of diaryl sulfides is the transition metal catalyzed CS coupling reaction. Herein we report a study on the iron-catalyzed protocol for cross-coupling reaction of aryl halides with thiols. Structurally diverse diaryl sulfides were prepared efficiently by using a catalyst system involving cheap and environment-friendly FeCl3 and non-toxic universal ligandl -proline. The reaction mechanism for the iron-catalyzed CS coupling reaction was investigated by means of density functional theory (DFT) methods on a model system. The calculations were performed using hybrid PBE1PBE functional in conjugation with the LANL-2DZ basis set. The key step involved in the mechanism is the formation of a reactant complex in which both reactants are electrostatically bound to Fe(III) proline complex catalyst. The elimination of HI occurs with a much lower TS energy (20.0 kcal/mol) than the uncatalyzed reaction (44.7 kcal/mol).