Phosphoramidates special

Since 1973, many Lewis acid-catalyzed aldol reactions have been studied, as described above. There have, however, been few examples of Lewis base-catalyzed aldol reaction using special silyl enolates, e.g. phosphoramide-catalyzed aldol reactions of trichlorosilyl enolates 69 (Eq. (36)) [47] and CaCh-catalyzed reactions of dimethylsilyl enolates 72 in aqueous DMF (Eq. (37)) [56]. 

Dihydroxyarenes yield dioxaphospholes with PCI3. A special subclass of phosphite reactions are phosphitylations. Dichlorophosphite derived from PCI3 and an alcohol, epoxide, or P(OMe)3 are common phosphitylation reagents. Replacement of the alcohol by an amine leads to dialkylaminodichlorophos-phites and subsequent phosphoramidation of the substrate. Direct phosphitylation with PCI3 is useful with sterically hindered axial hydroxy functions which fail to phosphorylate with other reagents (eq 2). ... 

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