Functionalization of [60]Fullerene and of [60]Fullerene Monoadducts by Photochemical Cycloaddition of 4‐Methyl‐1,2,4‐triazoline‐3,5‐dione

Abstract

The photoreactions of 4‐methyl‐1,2,4‐triazoline‐3,5‐dione (NMTAD) with C60 and with several fullerene derivatives have been studied. In general, NMTAD cycloadds to C60 and to its monoadducts with closed structures in a highly regioselective [2+2] fashion at a cis‐1 [6,6] double bond. Cycloadditions to azafulleroids occur by a slightly different pathway and result in partially cluster‐opened bis(adducts). 1,6‐Methano[60]fulleroid, however, also undergoes a [2+2+2] cycloaddition in the absence of light. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Mechanistical Insights into the Bioconjugation Reaction of Triazolinediones with Tyrosine

“…Triazolinediones, such as 4-phenyl-3 H -1,2,4triazole-3,5­(4 H )-dione (PTAD), are very useful reagents in chemistry which are used in thermo- − as well as photochemical reactions. − PTAD is also an important tool for mass spectrometry analysis, for example, for identifying fatty acids. , In 2009, Barbas and co-workers extended the application range of cyclic diazodicarboxamides. They published the first report of selective bioconjugation at native tyrosine residues of proteins using cyclic diazodicarboxamides, specifically 4-phenyl-3 H -1,2,4triazole-3,5­(4 H )-dione (PTAD) .…”

23 Fullerenes

“…53 [60]Fullerene and mono-adducts of [60]fullerene react with 4-methyl-1,2,4-triazoline-3,5-dione; the latter resulting in highly regioselective addition to a double bond adjacent (a so called cis-1 bond) to the original site of addition. 54 Chiral HPLC has been used to separate a series of chiral bis-adducts of [60]fullerene. 55 The absorption spectra of several monoand bis -pyrrolidine adducts of [60]fullerene have been recorded and the visible region of the spectra shown to be significantly modified by the addition pattern observed in the fullerene derivative.…”

Water‐Involved Ring‐Opening of 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione for “Photo‐Clicked” Access to Carbamoyl Formazan Photoswitches In Situ

“…[9,10] In contrast to aliphatic [11][12][13] and aromatic [5][6][7][8][9][10] azo compounds, the N=N double bond harbored in azodicarbonyl exhibit unique reactivities due to the lowered LUMO energy, [14] providing an access to valuable heterocyclic frameworks through pericyclic reactions. High reactivity of triazolinediones (RTADs), especially 4-methyl-1,2,4-triazoline-3,5dione [15][16][17] and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), [14,18,19] are ascribed to the cyclic structure with further lowered LUMO energy of the N=N bond that are capable of mimicking the reactivity of singlet oxygen [20] or nitroso [21] in ene-type reactions, [22][23][24] [4 + 2] and [2 + 2] cycloadditions (Figure 1a). [25][26][27][28][29][30] Moreover, RTADs were easily attacked by amines to furnish ring-opening species which releases nitrogen to form urea [31,32] or dimerized bicyclic adduct (Figure 1b).…”