Carbon-phosphorus bond formation imine addition

Because organophosphorus compounds are important in the chemical industry and in biology, many methods have been developed for their synthesis [1]. This chapter reviews the formation of phosphorus-carbon (P-C) bonds by the metal-catalyzed addition of phosphorus-hydrogen (P-H) bonds to unsaturated substrates, such as alkenes, alkynes, aldehydes, and imines. Section 5.2 covers reactions of P(lll) substrates (hydrophosphination), and Section 5.3 describes P(V) chemistry (hydrophosphorylation, hydrophosphinylation, hydrophosphonylation). Scheme 5-1 shows some examples of these catalytic reactions. 

Heteroatom Wittig chemistry also includes reactions of N-sulfonyl imines. It was demostrated that these compounds underwent olefination reactions with nonstabilized phosphonium ylides under mild conditions to afford an array of both Z- and E-isomers of 1,2-disubstituted alkenes, allylic alcohols, and allylic amines.Additionally, studies of the reactions of 5-bromo-4,6-dimethyl-2-thioxo-l,2-dihydropyridine-3-carboni-trile and thiazolidinone with phosphorus ylides have proved the formation of new phosphonium ylides. Annulations via P-ylides are a common occurrence in the literature. For example, on photochemical irradiation, phosphonium-iodonium ylides were shown to undergo 1,3-dipolar cycloaddition reactions with triple bonds, via a carbene intermediate, to yield furans. " Even more common are the reactions of Morita-Baylis-Hillman (MBH) acetates and carbonates. Zhou et al. demostrated that these substrates were able to generate very reactive 1,3-dipoles in the presence of tertiary phosphines the dipoles then underwent cycloaddition reactions to yield annulation products (Scheme 16). ... 

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