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

Electron-deficient 1- and 2-azabuta-1,3-dienes are reagents intrinsically able to provide a wide range of cyclic and acyclic N-containing building blocks. Depending on their substitution, they behave as dienes for Diels-Alder reactions, as partners for [4+1], [3+2], [2+2]-cycloadditions, for aziridinations and as electrophiles for 1,2 and 1,4-additions. Nowadays, they are a very versatile family of compounds, despite their usual instability and complex reactivity.

One-pot tandem 1,4-1,2-addition of phosphites to quinolines.

Trialkyl and silylated dialkyl phosphites were evaluated as phosphorus nucleophiles for the addition to quinolines in a strong acidic medium allowing consecutive 1,4- and 1,2-addition breaking up the aromatic stabilisation, thereby leading to 2,4-diphosphono-1,2,3,4-tetrahydroquinolines in one single reaction step in moderate to good yields (2-84%).

Double nucleophilic 1,2-addition of silylated dialkyl phosphites to 4-phosphono-1-aza-1,3-dienes: synthesis of gamma-phosphono-alpha-aminobisphosphonates.

gamma-Phosphono-alpha-aminobisphosphonates were synthesized from a new class of 4-phosphono-1-aza-1,3-dienes by the addition of dialkyl trimethylsilyl phosphites to these azadienes in the presence of acid. Depending on the steric demand of the group on nitrogen, double 1,2-addition or tandem 1,4-1,2-addition occurred.