Synthesis of Pyrimidines Bearing Sterically Demanding Substituents from Azetes and Nitriles¹

2,2,2-Trifluoroacetaldehyde O-(Aryl)oxime: A Precursor of Trifluoroacetonitrile

“…As a highly reactive electrophilic reagent, trifluoroacetonitrile (CF 3 CN) has been utilized successfully for the synthesis of various trifluoromethylated nitrogen-containing heterocyclic derivatives, such as pyridines, pyridinones, pyrimidinones, pyrimidines, tetrazoles, tetraazapentalenes, imidazoles, and uracil . However, CF 3 CN is a highly toxic gas (boiling point of −64 °C), which is hard to handle for the development of reactions.…”

Cyanogen: A Versatile Reagent for Diversity-Oriented Synthesis

“…55 Initially formed salts 18-1 were then converted into highly energetic 5-cyanotetrazolates, representing nitrogen-rich cations (Scheme 18). Likewise, cycloaddition reactions of little importance, of azetes, 56 bis(triphenylphosphoranylidene)iminium azide, 57 and bis(germaethene) 58 with cyanogen were reported. Choi and Lim focused on a theoretical study describing the cycloaddition reaction of cyanogen on a Si(100)-2×1 surface.…”

Electron-deficient 1- and 2-azabuta-1,3-dienes: a comprehensive survey of their synthesis and reactivity

“…The synthesis of this azetine 303 was achieved by a 1,4-addition of a nitrile 302 to a kinetically stabilized azete 301 (Scheme 92). 162 The use of a whole range of polyalkoxycarbonylated 2-azabuta-1,3-dienes 305 in pericyclic reactions was studied by Palacios and co-workers. The preparation of these 2-azabuta-1,3-dienes 305 was accomplished by an aza-Wittig reaction between appropriate phosphazenes and carbonyl compounds.…”