Friedel–Crafts acylation of antiaromatic norcorroles: electronic and steric modulation of the paratropic current

Abstract

Acyl chlorides react with norcorrolatonickle(II) in dichloromethane in the presence of AlCl3 at room temperature affording two isomeric monoketone derivatives in moderate yields. For acetyl chloride, also diketones were detected...

1,3-Dipolar cycloaddition of polycyclic azomethine ylide to norcorroles: towards dibenzoullazine-fused derivatives

“…It is evident that deshielding above the macrocycle is strongly reduced in monoadduct 4 (∼24.7 ppm) as well as in diadducts 3 (7.7–12.4 ppm) and 5 (10.5–12.5 ppm) when compared with starting 1 -H, for which NICS(1) of about 31 ppm has been reported. 37,47 A similar paratropic ring current decrease has been found for di- or tetrahydrogenated nickel( ii ) norcorrole 48 as well as for a dihydropyrrazolo-fused cycloaddition product. 19 Conversely, a significant increase of NICS(1) up to 35–40 ppm for the dibenzoullazine-containing system 6 is observed, clearly related with the restoration of the full 20-π-electron (4 n + 4) pool and with aromatization of the fused polycyclic system.…”

Functionalization of 10-azacorroles: nitration, bromination and acylation

“…In contrast, C-acylation occurred exclusively at the C8 position proximal to the NH group to give β-acetylazacorrole through electrophilic substitution in the presence of zinc metal. Based on the Friedel-Crafts acylation of an antiaromatic norcorrole reported by us previously, 62 we explored the acylation of 10-azacorroles 1 with acid chlorides catalysed by a Lewis acid (AlCl 3 ). The reaction conditions and reaction time were different from those applied by Shinokubo et al 36 We employed several different acid chlorides in the reaction with compounds 1 comprising various N-aryl substituents for the formation of acylated azacorroles.…”

Progress in the Synthesis and Derivatization of Norcorrole

“…在 2016 年, 我们课题组 [41] 镍(II)去甲咔咯还能在路易斯酸的催化下的与酰氯 发生亲电取代反应. 2021 年, 我们课题组报道了在三氯 化铝(AlCl 3 )的存在下, 镍(II)去甲咔咯与芳基酰氯和烷 基酰氯进行弗里德-克拉夫茨(酰化)反应(Friedel-Crafts reaction) [43] ,…”