TEMPO-Mediated Synthesis of Tetrahydropyridinofullerenes: Reaction of [60]Fullerene with α-Methyl-Substituted Arylmethanamines and Aldehydes in the Presence of 4-Dimethylaminopyridine

Abstract

A series of scarce tetrahydropyridinofullerenes were synthesized by the metal-free-mediated reaction of [60]fullerene with cheap and easily available α-methyl-substituted arylmethanamines and aldehydes in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-dimethylaminopyridine (DMAP) in moderate to good yields comparable to the previously reported data for most monoadducts. The in situ generation of azadienes played a crucial role in the successful synthesis of tetrahydropyridinofullerenes. A plausible reaction mechanism was proposed to elucidate the reaction process.

Fullerotetrahydroquinolines: TfOH/TsOH ⋅ H2O‐Mediated One‐Pot Two‐Step Synthesis and N‐Alkylation/Acylation/Carboamidation Reaction

“…This requires new techniques to synthesize fullerotetrahydroquinolines, especially for the unreported N ‐unsubstituted fullerotetrahydroquinolines. We previously investigated the reactions of C 60 with cheap and readily available aldehydes and amines to produce a plethora of fulleropyrrolidines, [7] fulleropyrrolines, [8] tetrahydropyridinofullerenes, [9] fulleropyrrolidin‐2‐ols, [10] and cyclopentafullerenes [11] . In efforts to extend the fullerene reactions with aldehydes and amines, herein we describe the synthesis of scarce N ‐unsubstituted/substituted fullerotetrahydroquinolines without a directly attached nitrogen atom by the facile one‐pot two‐step reaction of C 60 with arylamines and paraformaldehyde promoted by trifluoromethanesulfonic acid (TfOH) and p ‐toluenesulfonic acid monohydrate (TsOH ⋅ H 2 O) and also disclose the further conversion of N ‐unsubstituted fullerotetrahydroquinolines into N ‐substituted fullerotetrahydroquinolines via the simple N ‐alkylation/acylation/carboamidation reactions.…”

Selective formation of dihydrofuran fused [60] fullerene derivatives by TEMPO mediated [3 + 2] cycloaddition of medium chain β-keto esters to C60

“…TEMPO acts either as a radical scavenger or as an oxidant. 25,26 We proposed that in these reactions, TEMPO efficiently oxidized radical 6 into cation 7. Based on the above experimental results and literature data, reaction mechanism pathway involving fullerenyl cation is proposed (Scheme 3).…”

TEMPO-Mediated Synthesis of Indolyl/Imidazo[1,2-a]pyridinyl-Substituted para-Quinone Methides from Butylated Hydroxytoluene

“…On the other hand, TEMPO (2,2,6,6-tetramethylpiperidine- N -oxyl), a stable organic nitroxyl radical, has been found as an efficient and effective catalyst in oxidative C–H functionalization reactions in recent years due to its versatile catalytic activity . In a study on mechanistic investigation of TEMPO-mediated hydroxyfluoroalkylation of indoles and imidazo­[1,2- a ]­pyridines in the presence of BHT, we observed the formation of the indole-substituted p -QM .…”