Borane catalysed annulative sulfenylation of internal alkynes: towards the synthesis and study of fused heterocycles

Abstract

Herein, we disclose a B(C₆F₅)₃-catalysed intramolecular cyclisation reaction of N-protected alkynyl anilines and phenols to generate 5-membered heterocycles, including 3-sulfenyl indoles (17 examples, up to 91% yield) and benzo[b]furans (9 examples, up to 90% yield), in good yields with several functional group tolerances. This protocol was adapted into an annulative π-extension (APEX) reaction when using diyne derivatives of aniline and phenol, which effectively led to sulfenylated polyaromatic heterocycles, such as benzo[a]carbazole or naphtho[1,2-b]benzofurans. These products exhibit fluorescence from locally excited states, consistent with their large singlet-triplet energy gaps. Additionally, the cyclisation of aryl propargyl ethers, 4-diphenylbut-1-yne and a tosyl-protected propargylaniline afforded sulfenylated 6-membered products (7 examples, up to 94% yield). Density functional theory (DFT) calculations, corroborated by initial kinetics, helped to understand the order and rate of the reaction and support a mechanism in which thiirenium ions are involved as key intermediates in the formation of the observed products.