613-15-0Relevant articles and documents
Radical and ionic mechanisms in rearrangements of o-tolyl aryl ethers and amines initiated by the Grubbs-stoltz reagent, et3SiH/KOtbu
Kolodziejczak, Krystian,Murphy, John A.,Stewart, Alexander J.,Tuttle, Tell
, (2021/12/04)
Rearrangements of o-tolyl aryl ethers, amines, and sulfides with the Grubbs-Stoltz reagent (Et3SiH + KOtBu) were recently announced, in which the ethers were converted to o-hydroxydiarylmethanes, while the (o-tol)(Ar)NH amines were transformed into dihydroacridines. Radical mechanisms were proposed, based on prior evidence for triethylsilyl radicals in this reagent system. A detailed computational investigation of the rearrangements of the aryl tolyl ethers now instead supports an anionic Truce-Smiles rearrangement, where the initial benzyl anion can be formed by either of two pathways: (i) direct deprotonation of the tolyl methyl group under basic conditions or (ii) electron transfer to an initially formed benzyl radical. By contrast, the rearrangements of o-tolyl aryl amines depend on the nature of the amine. Secondary amines undergo deprotonation of the N-H followed by a radical rearrangement, to form dihydroacridines, while tertiary amines form both dihydroacridines and diarylmethanes through radical and/or anionic pathways. Overall, this study highlights the competition between the reactive intermediates formed by the Et3SiH/KOtBu system.
Cu-catalyzed cascade reaction of isoxazoles with diaryliodonium salts for the synthesis of acridines
Li, Jian,Lu, Xuechen,Xu, Qiuneng,Yan, Shenghu,Zhu, Shangrong
, p. 944 - 950 (2020/12/23)
A straightforward and efficient synthesis of acridine derivatives via a copper-catalyzed cascade reaction among isoxazoles and diaryliodonium salts is achieved. Various mono-, multi-substituted and 9-substituted acridine derivatives could be obtained in moderate to good yields. The process has gone through tandem double arylation and Friedel-Crafts reactions.
Nitrogen-Iodine Exchange of Diaryliodonium Salts: Access to Acridine and Carbazole
Wang, Ming,Fan, Qiaoling,Jiang, Xuefeng
, p. 216 - 219 (2018/01/17)
A nitrogen-iodine exchange protocol of diaryliodonium salts with sodium azide salt is developed for general construction of significant functional acridines and carbazoles, in which introduction of nitrogen at a late stage was successfully established avoiding heteroatom incompatibility. Inorganic sodium azide served as the sole nitrogen atom source in this transformation. The diversiform functional acridines and carbazoles were comprehensively achieved through annulated diaryliodonium salts, respectively. Notably, Acridine orange (a fluorescent indicator for cell lysosomal dye) and Carprofen (a nonsteroidal anti-inflammatory drug) were efficiently established through this protocol.