A new synthesis of aziridine-2-carboxylates by reaction of hexahydro-1,3,5-triazines with alkyldiazoacetates in the presence of tin(IV) chloride

Six‐Membered Heterocycles: Triazines, Tetrazines and Other Polyaza Systems

“…N-Methyleneamine equivalents can be generated in situ from hexahydro-1,3,5-triazines 348 (Scheme 20.101) in the presence of a Lewis acid (LA) and reacted with various nucleophiles for the synthesis of aziridine 349 [692,693], azetidin-2-ones 350 [694,695], anilines 351 [696,697], tetrahydroquinolines 352 [697], 5-aminomethyl-dihydrofuran-2-ones [698], and anilinomethylazides [699]. Synthetic applications of N-methyleneamine equivalents were reviewed in 2002 [700].…”

Density functional studies on copper-catalysed asymmetric aziridination of diazoacetate with imines

“…Many non-catalytic pathways to aziridines have been developed [10,11]; recently however, the development of the asymmetric catalytic aziridinations has received the most attention [2]. A variety of methods have been developed for the synthesis of aziridines [9,12,13] including a ring closure reaction of 1,2-amino alcohols or their derivatives [14,15], ring opening of epoxides with metal azides [16,17], addition of a-haloester enolates to imines [18], transfer of a nitrene group to an alkene [19,20], and the reactions between diazo esters and imines mediate either by carbene transfer catalysts [21][22][23] or Lewis acid catalysts [24][25][26][27][28][29].…”

Rhodium(II)‐Catalyzed [4+2] Annulation of Ester‐Tethered 1‐Sulfonyl‐1,2,3‐Triazoles and Hexahydro‐1,3,5‐Triazines

“…[3] Since then, it has been utilized as a stable and sustainable imine surrogate in organic synthesis. Giumanini [4] and Ha [5] have made a significant contribution in this regard. In recent years, the application of hexahydro-1,3,5-triazines in organic synthesis has increased significantly.…”

“…Meanwhile, there is an equilibrium between hexahydro-1,3,5- triazine 2 and formadimine D at high temperature. [4][5][6][7][8][9][10][11] In path b, a stepwise [4 + 2] annulation between C and formaldimine D was carried out starting from an aza-Michael addition. In path c, the concerted pathway could also account for the final product.…”

“…Since the triazole and the catalyst were added after the completion of the reaction of p-toluidine and paraformaldehyde, no product of triazole and p-toluidine was detected. The hexahydro-1,3,5-triazine usually participated in the reaction in the form of formaldimine, [4][5][6][7][8][9][10][11] so the reaction of triazole 1 a and imine 12 was carried out. The annulation product 13 was obtained in only 29% yield (Scheme 4e).…”