Copper-Catalyzed Alkyne−Aryne and Alkyne−Alkene−Aryne Coupling Reactions

Abstract

The efficient copper-catalyzed two-component coupling reaction of alkynes with arynes and the three-component coupling reaction of alkynes with allylic chlorides and arynes have been developed. Copper acetylide was postulated as a transient intermediate for the initiation of the coupling reactions.

Synthesis and application of a novel bis-1,2,3-triazole ligand containing a 2,2'-bipyrrolidine core

“…The 1 H and 13 C NMR spectra for this internal alkyne matched identically to the many previous reported syntheses. 14,15,16 Synthesis of ethyl 5-phenyl-1H-1,2,3-triazole-4-carboxylate (3). To a gently stirred solution of alkyne 2 (1.75 g, 10 mmol) in DMSO (20 mL, 0.5 M) was added NaN 3 (1.9 g, 30 mmol) in four portions over 20 minutes.…”

O ressurgimento da química de benzino com sililaril triflatos no contexto das reações de inserção em ligações sigma

“…29 A reação de inserção de arinos em ligações sigma carbono-metal (C-M) de reagentes organometálicos, pode ser virtualmente exemplificada pelo trabalho de Zhang e colaboradores, que envolve a reação entre sililaril triflatos (2) e alcinos terminais (54) na presença de CuI e CsF, considerando essencialmente a formação in situ de acetiletos de cobre (I), 30 resultando no isolamento de alcinos dissubstituídos (55) 31 (Esquema 23).…”

“…31 Este pressuposto foi reforçado por resultados recentemente publicados por Yoshida e colaboradores. 32 Larock e colaborador estudaram extensivamente reações de Narilação de aminas e sulfonamidas, bem como reações de O-arilação de fenóis e ácidos arilcarboxilílicos, as quais podem ser formalmente consideradas como reações de inserção de arinos em ligações sigma heteroátomo-hidrogênio (Het-H) [33][34][35] (Esquemas 25 a 28).…”

Gold-catalyzed cyclotrimerization of arynes for the synthesis of triphenylenes

“…To our knowledge, there are many methods for triphenylene formation via arynes. For examples, the cyclotrimerization of benzyne catalyzed by Cu(I) (20 mol%) afforded triphenylene in refluxing CH 3 CN (Scheme 1) [26], and triphenylenes were also isolated during attempts at obtaining a metal complex of arynes [27][28][29][30]. The efficient preparation of triphenylenes with a catalytic amount of promoters is still a demand to fulfill the modern synthesis.…”

“…We have been interested in studying gold-catalyzed cyclotrimerization of arynes (active π-components), which have seldom served as the substrate for gold catalysis [9,26]. Herein, we report that the use of PPh 3 AuCl as the catalyst for the cyclotrimerization of arynes provides a convenient and general approach to triphenylenes under mild conditions (Scheme 1).…”