Stereoselective Aminoiodination of Activated Alkynes with Organoiodine(III) Reagents and Amines via Multiple‐Site Functionalization: Access to Iodinated Enamines and N‐Aryl Indoles

Abstract

A stereoselective aminoiodination of activated alkynes with PhI(OAc) 2 and amines via multiple-site functionalization to afford (Z)diethyl 2-(diphenylamino)-3-iodomaleate derivatives with superior yields has been described. The key feature of this reaction is the incorporation of iodide and aryl group concurrently in the same molecule in a stereoselective manner by employing PhI(OAc) 2 as electrophilic reagent as well as iodide and aryl group source. The high stereoselectivity of the reaction can be explained based on the structure of the possible intermediates, the conformations of which controlled by the hydrogen bonding, steric hindrance and electrostatic attrac- [a] We choose diethyl acetylenedicarboxylate 1a, aniline 2a and phenyliodine(III) diacetate (PIDA) 3a as the model substrates to

Haloamines as Bifunctional Reagents for Oxidative Aminohalogenation of Maleimides

“…Overall, this one-pot multicomponent reaction not only provides a rapid and efficient method to access the aminohalogenated maleimides with the formation of C–N and C–X (X = Cl, Br, I) bonds but also offers a facile approach to install drug-containing secondary amines into maleimide skeletons to advance novel drug research. Most importantly, in-situ-generated N–I bonds were used as difunctionalized reagents and enabled the synthesis of iodinated enamines that were difficult to access or inaccessible by previous methods …”