Interplay between nitronates and nitriles accomplished in a PtIV-mediated reaction

Unexpectedly efficient activation of push–pull nitriles by a PtII center toward dipolar cycloaddition of Z-nitrones

“…7 Although a rather wide variety of allyl-[acyclic nitrones (A, Fig. 1), 8-13 cyclic nitrones such as pyrroline-N-oxide (B), [14][15][16] imidazoline-N-oxides (C), 7 oxazoline-N-oxides (D), 17 and nitronates (E) 18 ] and propargyl/allenyl-[azides (F) 6,19- 22 and nitrile oxides (G) 23,24 ] anion type dipoles have been applied for metalmediated DCA to nitriles, the range of employed RCN substrates is usually restricted to the conventional species such as alkyl-and arylnitriles. Application of DCA in another important category of nitrile substrates, the so-called push-pull nitriles (a push-pull system is highly polarized and it is characterized by an electronwithdrawing substituent or electronegative atom on one side of the multiple bond and an electron-donating substituent on the other side), 25-27 e.g.…”

Metal‐Catalyzed Synthesis of Functionalized 1,2,4‐Oxadiazoles from Silyl Nitronates and Nitriles

“…Silver(I) as catalyst can coordinate and activate the nitrile and the silyl nitronate as well. Noteworthy is the difference of the Ag‐mediated oxadiazole formation described here to the Pt(IV)‐mediated reaction of cyclic nitronates and alkyl nitriles, where no cycloaddition had occurred …”

Zinc(ii)-mediated generation of 5-amino substituted 2,3-dihydro-1,2,4-oxadiazoles and their further ZnII-catalyzed and O2-involving transformations

“…Similar ring cleavage is proposed as one of key steps in the Pt IV -mediated reaction of a propiononitrile ligand with cyclic nitronates, leading to formamidine platinum(IV) complexes. 42 We assume a similar mechanism for the observed ring-opening reaction (route K; 4ea).…”

“…Taking into account our interest to metal-mediated reactions of nitrile substrates 1,[29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] and, in particular, to metal-mediated 1,3-dipolar cycloaddition, 1,[14][15][16]42,43,45,46 we focused our efforts on the search for a practically useful system for the generation of metal-free DHODs and we applied a labile metal, i.e. zinc(II), as an activator.…”