Electrophilic Oxythio/selenocyanation of o‐Alkenyl Benzoic Acids: Divergent Synthesis of Thio/selenocyanated Isobenzofuranones and Isocoumarins

Abstract

A transition-metal free thio/selenocyanation of oalkenyl benzoic acids via the electrophilic ClÀ S(Se)CN species, in-situ generated from inorganic thio/selenocyanating salt and PhICl 2 , has been realized under mild reaction conditions. This protocol offers a divergent synthesis of thio/selenocyanated isobenzofuranones and isocoumarins, depending on the substitution type of the substrates.

Synthesis of 4-Functionalized Pyrazoles via Oxidative Thio/selenocyanation Mediated by PhICl2 and NH4SCN/KSeCN

“…On the other hand, organic thiocyanates usually are served as useful synthetic intermediates that could be conveniently converted to sulfur-containing derivatives including sulfides [24], 3 disulfides [25], thiocarbamates [26] and trifluoromethyl thioethers [27]. Likewise, selenocyanates can be used as versatile precursors for the synthesis of a variety of selenium-containing compounds [28][29][30][31][32].…”

Synthesis of 4-functionalized pyrazoles via oxidative thio- or selenocyanation mediated by PhICl2 and NH4SCN/KSeCN

“…On the other hand, organic thiocyanates usually serve as useful synthetic intermediates that can be conveniently converted to sulfur-containing derivatives including sulfides [ 24 ], disulfides [ 25 ], thiocarbamates [ 26 ], and trifluoromethyl thioethers [ 27 ]. Likewise, selenocyanates can be used as versatile precursors for the synthesis of a variety of selenium-containing compounds [ 28 – 32 ].…”

Selenonium Salt as a Catalyst for Nucleophilic Substitution Reactions in Water: Synthesis of Thiocyanites and Selenocyanates

“…Not surprisingly, the search for methods to prepare these valuable compounds has attracted much attention. They can be prepared, for instance, with the aid of phase transfer catalysts [ 27 , 28 , 29 , 30 , 31 ], in free radical reactions [ 32 , 33 , 34 , 35 ], by electrophilic addition to suitable organic substrates [ 36 , 37 ], or in reactions employing ionic liquids as a solvent and the nucleophilic source of chalcogen cyanide [ 38 ]. In this contribution, we share our findings on the use of selenonium salts to activate substrates such as benzyl bromides through chalcogen bond interactions, facilitating the displacement reaction with KChCN (Ch = S or Se) using a 20:1 mixture of water and dimethyl carbonate as a solvent.…”