14372-67-9

Upstream product

• 1111-67-7 copper(I) thiocyanate 
• 536-90-3 m-Anisidine 
• 333-20-0 potassium thioacyanate 
• 15570-12-4 3-methoxybenzenethiol 
• 1147550-11-5 ammonium thiocyanate 
• 17333-78-7 3-methoxyphenyldiazonium ion 
• 540-72-7 sodium thiocyanide 
• 2290-65-5 trimethylsilyl isothiocyanate 
• 10365-98-7 3-methoxyphenylboronic acid 

Downstream Products

• 1333375-76-0 1-[(difluoromethyl)thio]-3-methoxybenzene 
• 97675-15-5 1-(methoxy)-3-[(trifluoromethyl)thio]benzene 
• 3097-21-0 1,3-dimethyl-1,3-dihydrobenzimidazol-2-one 
• 59014-89-0 bis(3-methoxyphenyl)disulfide 

Relevant academic research and scientific papers

Triphenylbismuth Dichloride-Mediated Conversion of Thioamides to Nitriles

Thioamides were efficiently converted to nitriles using the pentavalent triphenylbismuth dichloride in combination with triethylamine. The reaction involved the dehydrosulfurization of primary thioamides to afford substituted aromatic or aliphatic nitriles in good to excellent yields. The process was also successfully extended to the synthesis of cyanamides starting from the corresponding thioureas and of thiocyanates from dithiocarbamates.

Direct Photocatalytic S-H Bond Cyanation with Green cN Source

Herein we report a novel C-S bond cleavage and reconstruction strategy for the synthesis of thiocyanates through direct photocatalytic S-H bond cyanation from thiols and inorganic thiocyanate salts. In our strategy, the unprecedented example of cutting off C-S bond of SCN- to deliver the green CN sources is demonstrated. This transformation features nontoxic and inexpensive CN sources, available starting materials, metal-/base-/ligand-/peroxide-free, high step economy and mild conditions. It leads to the construction of various thiocyanates and some medicinally and biologically active thiocyanate-containing molecules.

One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)

An efficient one-pot cascade methodology for the synthesis of (ethoxycarbonyl)difluoromethyl thioethers is described. Benzyl, allyl, alkyl halides or diazonium salts as the starting materials together with thiocyanate sodium and TMS-CF2CO2Et in the presence of CsF or NaOAc afford a variety of the fluoroalkylthiolated products in moderate to good yields.

Iron-Catalyzed Decarboxylation of Trifluoroacetate and Its Application to the Synthesis of Trifluoromethyl Thioethers

Nucleophilic CF3 has been generated by decarboxylation of potassium trifluoroacetate, arguably the most easy-to-handle, inexpensive, and sustainable source of trifluoromethyl groups. Simple iron(II) chloride catalyzes the decarboxylation as well as a subsequent trifluoromethylation of organothiocyanates, resulting in a straightforward synthesis of trifluoromethyl thioethers. The KCN byproduct is absorbed by iron(II) with formation of nontoxic potassium hexacyanoferrate. An analogous trifluoromethylation of aldehydes with trifluoroacetate underlines the synthetic potential of such iron-catalyzed decarboxylative trifluoromethylations.

Synthesis of difluoromethyl thioethers from difluoromethyl trimethylsilane and organothiocyanates generated in situ

A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts. This strategy enables the introduction of difluoromethylthio groups - a largely unexplored substituent with highly promising properties - into drug-like molecules. A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts.

General and practical formation of thiocyanates from thiols

A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.

A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS

A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups.

Synthesis of aryl thiocyanates via copper-catalyzed aerobic oxidative cross-coupling between arylboronic acids and KSCN

A new protocol for the preparation of aryl thiocyanates by the cross-coupling reaction of arylboronic acids with KSCN salt is described. The coupling reaction was catalyzed by 20 mol% of copper acetate in the presence of 2.0 equivalents 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. A variety of arylboronic acids, including those with substituents at ortho position, were suitable under the reaction conditions. Georg Thieme Verlag Stuttgart · New York.

Improved procedure to aryl thiocyanates: A new synthetic application of dry arenediazonium o-benzenedisulfonimides

Aryl thiocyanates 3 (22 examples) were easily prepared by reaction of dry arenediazonium o-benzenedisulfonimides 1 and sodium thiocyanate (2) in anhydrous acetonitrile at room temperature (20-25 °C) in the presence of copper powder (Procedure A) and at 50 °C or room temperature without the metal catalyst (Procedure B). The yields were from very good to excellent in Procedure A (average yield = 83%), and from modest to excellent in Procedure B (average yield = 63%). In comparison with the thiocyanod-ediazoniation carried out under traditional Sandmeyer-type conditions, the yields of 3 were higher and the isothiocyanate isomers were formed only in traces. Moreover, the results obtained in the absence of copper confirm the role of the anion of salts 1 as an electron transfer agent.