Ultra-fast Suzuki and Heck reactions for the synthesis of styrenes and stilbenes using arenediazonium salts as super-electrophiles

Abstract

The reliable and convenient procedure for the ultrafast conversion of potassium vinyltrifluoroborate to stilbenes and styrenes with impressive TOFs is proposed.

Multibond Forming Tandem Reactions of Anilines via Stable Aryl Diazonium Salts: One-Pot Synthesis of 3,4-Dihydroquinolin-2-ones

“…These were prepared from anilines using a polymer-supported nitrite reagent under mild conditions and were found to have particularly high thermal and aging stability. Despite these properties, aryl diazonium tosylate salts are still reactive and have been utilized in standard substitution and cross-coupling reactions. , We recently demonstrated that aryl diazonium tosylate salts could be generated in situ and subjected to an iodination reaction for the one-pot tandem synthesis of aryl iodides from anilines . Because of the relatively stable nature of aryl diazonium tosylate salts and this initial demonstration of their application in one-pot tandem processes, we were interested in further exploiting these compounds for additional multistep transformations.…”

Synthesis of Structurally Diverse Benzotriazoles via Rapid Diazotization and Intramolecular Cyclization of 1,2‐Aryldiamines

“…Another key objective was to show that the use of a polymer‐supported nitrite reagent would facilitate work‐up and purification of the benzotriazole product. In this study, the polymer‐supported nitrite reagent was prepared by ion exchange of the tetraalkylammonium functionalized resin, Amberlyst A‐26 with an aqueous solution of sodium nitrite . Following our previous work, diazotization and cyclization of 1a was attempted using 3 equivalents of both the polymer‐supported nitrite reagent and p ‐tosic acid in acetonitrile at 80 °C.…”

“…In 2008, Filimonov and co‐workers showed that a polymer‐supported nitrite reagent in combination with less harsh acidic conditions ( p ‐tosic acid) could be used for the preparation of stable aryl diazonium tosylate salts . More recently, we have shown that this safe, mild and operationally simple method for aryl diazonium salt formation can be combined in one‐pot multistep processes for (radio)iodination and Heck–Matsuda reactions of anilines , . We now report a general synthesis of benzotriazoles from 1,2‐aryldiamines using a polymer‐supported nitrite reagent, under mild conditions (Figure e).…”

Recent Development of Aryl Diazonium Chemistry for the Derivatization of Aromatic Compounds

“…To expand the substrate scope of organoboron coupling partners, an ultrafast Pd-catalyzed coupling reaction of potassium vinyltrifluoroborate 151 was developed, facilitating the synthesis of styrenes that are prone to polymerization and the preparation of stilbenes within minutes through a Suzuki–Heck coupling sequence (Scheme ). The scope of the organoboron moiety can also be expanded to diarylborinic acids …”