Synthesis of biaryls from aryltriazenes

Abstract

Aryltriazenes react with aromatic solvents in the presence of trifluoroacetic acid to produce biaryls. The mechanism of the reaction involves the formation of arenediazonium trifluoroacetates which lose nitrogen to give mainly aryl radicals.

Guided desaturation of unactivated aliphatics

“…24–26 An underutilized tactic for generating aryl radicals is the reductive dissociation of aryl triazenes 27 in the presence of acid and catalytic metal salts. 28–30 Traditionally used as protecting groups for anilines 31 and linkers in solid-phase synthesis, 32 aryl triazenes can be prepared in high yields from the corresponding anilines and are stable to basic, reductive and alkylating conditions, even in complex settings. 33,34 In order to append an aryl triazene to alcohols and amines, a functionalized aryl sulfonyl chloride was deemed appropriate, thus leading to a triazene sulfonyl chloride ( o - T osyl Tria z ene Chloride, Tz o Cl, 21 ) as our portable desaturase of interest.…”

Meerwein arylation with 3-fluorobutenone

“…We have only found records of iodo-fluoro methanes and ethanes and some minor products from iodofluorination [9]. In comparison of the F NMR chemical shifts of products 9a-9f with a similar noniodinated compound [6], we find that the fluoro-iodo compounds are approximately 67 ppm downfield from hydro-fluoro compound.…”

“…The preparation of 7 [4] and of aryl triazines (8a-8f) [9] have been reported. (7) reacts with aryl triazenes in the presence of zinc iodide to give 4-aryl-3-fluoro-3-iodo-2-butanones (9a-9f) in moderate yields.…”

Facile and Efficient Reductive Homocoupling of Benzyl and Aryl Halides Catalyzed by Ionic Liquid [C12mim][CuCl2] in the Presence of Metallic Zinc and Copper

“…The usual synthetic methods for such a conversion include the Ullmann coupling [4][5][6], Suzuki coupling [7][8][9][10][11][12], Scholl reaction [13,14], Gomberg-Bachmann reaction [15,16], Stille reaction [17][18][19][20], and other couplings [21][22][23][24]. However, these above-mentioned protocols, in general, are invariably associated with one or more disadvantages, such as low yields, long reaction times, high reaction temperatures, high catalyst loading, tedious workup procedures, costly metal catalysts, difficulty of catalyst recovery, and environmental toxicity.…”