Transition Metal Catalyzed Synthesis of Aryl Sulfides

Abstract

The presence of aryl sulfides in biologically active compounds has resulted in the development of new methods to form carbon-sulfur bonds. The synthesis of aryl sulfides via metal catalysis has significantly increased in recent years. Historically, thiolates and sulfides have been thought to plague catalyst activity in the presence of transition metals. Indeed, strong coordination of thiolates and thioethers to transition metals can often hinder catalytic activity; however, various catalysts are able to withstand catalyst deactivation and form aryl carbon-sulfur bonds in high-yielding transformations. This review discusses the metal-catalyzed arylation of thiols and the use of disulfides as metal-thiolate precursors for the formation of C-S bonds.

Poly(N-bromo-N-ethyl-benzene-1,3-disulfonamide) and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide as new efficient reagents for one-pot synthesis of furano and pyrano pyrimidinones (thiones)

“…Replacing urea with thiourea produced the corresponding thio-40 derivatives in good yields (Table 2, entries 2, 4 and 6). 27 To test this type of MCR, the scope of the reaction was investigated with a series of aromatic aldehydes, urea/thiourea and 2,3-dihydrofuran in an effort to build up similar 4-arylhexahydrofuro[2,3-d]pyrimidin-2(1H)-ones 10 or 4-arylhexahydrofuro[2,3-d]pyrimidin-2(1H)-thiones (Table 3). The reason for low yields in producing the desired products with thiourea is probably due to the strong coordinating ability of sulfur often leads to the belief that 5 sulfur will hinder reagent activity.…”

Synthesis of diaryl thioethers from aryl halides and potassium thiocyanate

“…According to previous reports, we propose a mechanism for thioetherification of aryl halides with KSCN as shown in Scheme . First, an aryl halide is added to Pd(0) species through an oxidative addition step which causes Pd(II) formation.…”

Two‐Step Synthesis of Unsymmetrical Diaryl Sulfides by Electrophilic Thiolation of Non‐functionalized (Hetero)arenes

“…The abundance of natural products in which sulfur‐containing moieties are present, together with the number of applications that organosulfur compounds have found in seemingly unrelated fields such as drug development, organic materials, ligand design or polymer science, makes versatile methods to introduce sulfur containing moieties in organic molecules of enormous synthetic interest (Scheme a). Among these, the metal‐catalyzed cross‐coupling reaction between thiols and organic halides has attracted considerable attention since it allows the synthesis of unsymmetrically substituted aryl sulfides from easy available thiols and aryl halides or pseudohalides . Many advances have been achieved in this reaction, the replacement of the originally used Pd‐ and Ir‐based catalysts by more abundant first‐row transition metals probably being the most prominent one (Scheme b) .…”

“…Among these, the metal-catalyzed cross-coupling reaction between thiols and organic halidesh as attracted considerable attention since it allows the synthesis of unsymmetrically substituted aryl sulfides from easy available thiols and aryl halideso rp seudohalides. [6] Many advances have been achieved in this reaction, the replacement of the originally used Pd-and Ir-based catalysts [7] by more abundant first-rowt ransition metals probably being the most prominento ne (Scheme 1b). [8] In spite of this success, the employmento fm etal catalystsi sn ot always exempto fp roblems;t hey often suffer from the necessity of pre-functionalized substrates and, if they are used at late stages of as ynthesis, the possibility of contamination of the final product with toxic metal impurities is as eriousissue.…”