Hydrophosphonylation, reviews

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. 

A logical extension of these themes is for one catalyst to activate both the P-nucleophile and the unsaturated electrophile. This approach has been especially popular in asymmetric hydrophosphonylation of aldehydes and imines, which has been reviewed recently [59]. 

A review of asymmetric hydrocyanation, cyanosilylation, and hydrophosphonylation of carbonyl and imino groups covers catalyses by metals species, organics, and enzymes. ... 

It worth to mention that despite the importance of the Kabachnik-Fields reaction, stereoselective versions for the synthesis of enantioenriched a-aminophosphonates are scarce [212, 213], and only few enantioselective examples have been published to date (for reviews on enantioselective catalytic direct hydrophosphonylations of imines, see Refs. [162a-c]). Organocatalytic examples use well-known chiral binol-derived phosphoric acid organocatalysts (Fig. 12.6,80 and 81) [214], and regarding metal catalysis, chiral scandium(III)-A,A -dioxide and... 

Recent developments in metal-catalysed asymmetric addition of phosphorus nucleophiles, with the formation of P-C bonds, have been reviewed the metals and electrophiles have been discussed widely. DFT study of salicylaldehyde-Al(ni)-catalysed hydrophosphonylation of benzaldehyde by diethylphosphonate (DEPH) reveals that P-H activation by the formation of Al-phosphite species is followed by rate-determining C-P bond formation, which determines the predominant (S) configuration (with 99% ee) of the a-hydroxyl phosphonate ester on regeneration of the salicylaldehyde-Al(III) complexes. Reduction of activated carbonyl groups by alkylphosphanes can proceed either through path a or path b (Scheme 35), as evidenced experimentally and theoretically. ... 

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