Functions Containing at Least One Nitrogen and No Halogen or Chalcogen

Abstract

Of the functional groups covered in this chapter, by far the most common are the ketene aminals, accounting for approximately 50% of the literature in this area. Ketene aminals have been synthesized from a wide variety of functional groups, but the most popular methods involve the reaction of ketene dithioacetals or ketene N , S -acetals with relevant amines. In certain cases, prior oxidation of the ketene N , S -acetal is advantageous in order to introduce the second amine group. Methods have also been reported which avoid the release of foul smelling methylmercaptans. Improved methods of synthesizing ketene N , S -acetals as intermediates for the synthesis of mixed ketene aminals have been described. The syntheses of enamines and nitroalkenes bearing a variety of relevant α-substituents have been reported over the last decade including the first reported syntheses of gem -amido nitro alkenes and gem -alkoxycarbonylamino nitro alkenes. A large variety of functions containing one nitrogen functional group and various phosphorus functional groups have been reported, the most common being gem -amido phosphonio alkenes, gem -amido phosphorylalkenes, and α-phosphorylenamines. Several reports have been published on the synthesis of enamines containing silicon, palladium, chromium, tungsten, and tin at the α-position.