Activation of Aryl Thiocyanates Followed by Aryne Insertion: Access to 1,2-Thiobenzonitriles

Abstract

Palladium-catalyzed activation of carbon-sulfur bonds allows aryne insertion into aryl thiocyanates to generate new C-SAr and C-CN bonds in one step. The readily available starting materials make this method efficient in generating a variety of 1,2-thiobenzonitriles. By choosing an oxygen atmosphere the yields are increased and side reactions are minimized.

Catalytic Thiourea Promoted Electrophilic Thiocyanation of Indoles and Aromatic Amines with NCS/NH4SCN

“…[1,2] They also serve as synthetic intermediates or pseudohalides to access sulfur-containing compounds. [3][4][5][6][7][8][9][10][11][12][13][14] Thus, the introduction of a thiocyano group into a molecule is of significant importance. Over the past decades, tremendous efforts have been made in direct oxidative thiocyanation of (hetero)aromatic compounds including indoles, aromatic amines as well as other heterocycles.…”

Highly Selective Oxidation of Sulfides to Sulfones by H2O2 Catalyzed by Porous Capsules

“…However, in this work Mo 72 Fe 30 indicated low catalytic performance compared to other catalysts [25]. Interestingly, Mizuno discovered that the strong Lewis acidity of W atoms in polyoxometalate plays an important role in the oxidation [26]. As a result, following this work focused on the development of novel oxidation methods for the oxidation of organic compounds with polyoxometalates [27][28][29], a catalytic activity of Na 6 (NH 4 ) 20 In the present work, in order to optimize the reaction conditions for the selective oxidation of sulfides, the influence of temperature, hydrogen peroxide and catalyst amounts in acetonitrile as a solvent on the oxidation of thioanisole as a model substrate was studied (Figs.…”

Copper-catalyzed cyanothiolation to incorporate a sulfur-substituted quaternary carbon center

“…Conceivably, the development of cyanofunctionalization is extremely desirable in the construction of functionalized nitriles, 2 and it has caught increasing attention in the past decades. Previous cyanofunctionalizations generally required the cleavage of the RX–CN (X = Si, 3 Ge, 4 B, 5 Sn, 6 S, 7 O, 8 C, 9 or N 10 ) bond through oxidative addition of transition metal (M = Ni, Pd, Pt) complexes, and immediately, both functional fragments were simultaneously installed at disparate carbon atoms of versatile substrates, including arynes, alkenes and alkynes (Scheme 1a). However, a process to incorporate two cleaved functional fragments onto a single carbon atom via transition metal-catalyzed cyanofunctionalization has never been realized, and is still a challenging issue.…”