Aromatization modulates the activity of small organic molecules as promoters for carbon–halogen bond activation

Abstract

The indoline/t-BuOK/O2 system was found to exhibit unprecedented high reactivity for promoting the BHAS reaction of aryl bromides and chlorides.

Aromatization as the driving force for single electron transfer towards C–C cross-coupling reactions

“…From this evidence, we conclude that for the deprotonated heterocycles, the gain in aromaticity could be the driving force for SET, which essentially enables them as the initiator. Jiao has recently established a system where the gain of aromaticity has been pointed as the driving force for electron transfer from indoline, 48 finally converting the promoter to indole. As delineated through the mechanistic cycle (Scheme 2), at least two phenazine-based species are responsible to participate in SET.…”

Ground State Cross-Coupling of Haloarenes with Arenes Initiated by Organic Electron Donors, Formed in situ: An Overview

“…Likewise for 1,2-diamines 75, Murphy et al 15 proposed the formation of potassium salts of enediamines 76, and evidence for these species was reported by Jiao et al 25 Jiao's group refined the mechanism of the reaction of 1,2-diamines, and went on to illustrate their ideas proposing and verifying that ArNHMe 33 should act as precursor to organic electron donor 77. 39,40 With the hydroxymethylpyridine 34, strong evidence was amassed that the disalt 78 was produced 24 and was responsible for initiating the coupling reaction through electron transfer. Likewise, Mandal et al 19,20 established that phenalenone 35 was converted by KOtBu into electron donor radical dianion 79.…”

Potassium tert‐Butoxide‐Promoted Acceptorless Dehydrogenation of N‐Heterocycles

“…It should be noted that Jiao, et al. reported that trace amount of dioxygen facilitated the dehydrogenation of 2‐cyclopropylindoline in the presence of large excess of KO t Bu base (12 equiv), and under the dioxygen‐free conditions by means of a small N 2 flow with a positive pressure the indoline dehydrogenation reaction could be excluded . However, when indoline ( 3 a ) was used as the substrate under a slight N 2 flow with a positive pressure, the efficient formation of indole ( 4 a , 91%), was not affected, excluding the effect of air or O 2 .…”