Synthesis of α‐Amino Tertiary Alkylperoxides by Lewis Acid‐Catalyzed Peroxidation of 1,3,5‐Triazines

Abstract

α-Substituted peroxides have been found in natural products and are widely used as anti-malarial agents. Zn-(OTf) 2 -catalyzed peroxidation of 1,3,5-triazines has been developed, accessing diversely substituted α-amino tertiary alkylperoxides with high efficiency. Mechanistic investigations and useful synthetic application of the products have also been presented.

Structural and Dynamic Behaviour of Heterocycles Derived from Ethylenediamines with Formaldehyde: 1,3,5-Triazinanes and Bis(imidazolidinyl)methanes

“…In order to explore the versatility of formaldehyde in the synthesis of other six-membered heterocycles, the reactions of N-benzyl-amine in the presence of formaldehyde and sodium hydrosulphide in different proportions were explored. The equimolar reaction between N-benzylamine and formaldehyde led exclusively to the formation of N-benzyltriazinane (3, 98% yield), which has already been previously reported by other research groups under different reaction conditions [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44]. The reaction of one equivalent of Nbenzylamine with five of formaldehyde and three of sodium hydrosulphide was explored, obtaining a mixture of products in 50:50 ratios: N-benzyl-thiadiazinane (4) and Nbenzyl-dithiazinane (5).…”

“…13 15 N NMR (41 MHz, CDCl 3 ) δ: −327.6 (N1), −327.9 (N3). LRMS (EI, 20 eV), m/z (%): 335 (3), 292 (2), 251 (2), 220 (13), 205 (42), 175 (91), 161 (54), 146 (6), 132 (16), 119 (10), 99 (16), 91 (100), 83 (37), 72 (14), 57 (18), 42 (37) ), 4.17 (s, 4H, H2), 3.47 (s, 2H, H6), 3.42 (t, 4H, J = 6.6 Hz, H4), 3.13 (t, 4H, J = 6.6 Hz, H5). 13 C NMR (101 MHz, CDCl 3 ) δ: 146.7 (C i ), 129.4 (C m ), 116.5 (C p ), 111.8 (C o ), 74.5 (C6), 69.1 (C2), 51.0 (C5), 45.8 (C4).…”

A New Catalytic Method for the Synthesis of Cyclic Azaperoxides with High Cytotoxic Activity

“…[46][47][48][49][50][51][52] Recently the reaction of 1,3,5-triazine and tert-butyl hydroperoxide has been shown in the presence of Zn(OTf) 2 as a catalyst to obtain acyclic α-amino tertiary alkylperoxides. [53] However, the reaction of 1,3,5-triazinanes with OH acids such as hydrogen peroxide, gem-bishydroperoxides and 1,1'peroxybis (1-hydroperoxycycloalkanes) has not yet been reported.…”

“…Notably, 1,3,5‐triazinanes can serve as two‐, three‐, four‐, and six‐atom synthons to take part in various cycloaddition reactions for the synthesis of nitrogen heterocycles of different sizes [46–52] . Recently the reaction of 1,3,5‐triazine and tert‐butyl hydroperoxide has been shown in the presence of Zn(OTf) 2 as a catalyst to obtain acyclic α‐amino tertiary alkylperoxides [53] . However, the reaction of 1,3,5‐triazinanes with OH acids such as hydrogen peroxide, gem‐bishydroperoxides and 1,1′‐peroxybis(1‐hydroperoxycycloalkanes) has not yet been reported.…”