Copper-catalyzed aminoalkynylation of alkenes with hypervalent iodine reagents

Abstract

A copper-catalyzed aminoalkynylation reaction of alkenes is developed for construction of diverse azaheterocycles and installation of an alkyne group in one step, presenting broad applications in synthesis, bioconjugation, and molecular imaging.

Alkynylation of radicals: spotlight on the “Third Way” to transfer triple bonds

“…Wang and Shen described the aminoalkynylation of alkenes based on the copper catalyzed cyclization of tethered alkenyl Weinreb amides (Scheme 37, eqn (1)) 95. Radical intermediates could be generated through the thermal homolytic cleavage of alkyl–Cu( ii ) species.…”

Photocatalytic Umpolung ofN- andO-substituted alkenes for the synthesis of 1,2-amino alcohols and diols

“…[33][34][35][36][37] Their application in radical-mediated olen alkynylation has also been explored. [38][39][40][41][42] Recently, our group has exploited the nucleophilicity of the carboxylate group of EBX reagents in atomeconomical reactions such as the 1,1-oxyalkynylation of diazo compounds and the ring-opening/oxyalkynylation of thiiranes. [43][44][45][46] Therefore, EBX reagents appear ideally suited for the functionalization of radical cations due to their dual nucleophilic/somophilic nature.…”

Synthesis of Cyclic N‐Hydroxylated Ureas and Oxazolidinone Oximes Enabled by Chemoselective Iodine(III)‐Mediated Radical or Cationic Cyclizations of Unsaturated N‐Alkoxyureas

“…The group of Wang developed three copper-catalyzed cyclizations of unsaturated Nmethoxy amides, among which only featured two examples of ureas in each study. [16][17][18] The electrophiles can be O-benzoylhydroxylamines, or cyclic hypervalent iodine reagents. An amine, [16] an alkyne [17] or an azide [18] group can be introduced during the cyclization (Scheme 1c).…”