P(RNCH2CH2)3N:: Superbasic and catalytic cages

In contrast to acyclic P(NR2)(3), the title pro-azaphosphatrane cages (first reported from our laboratories) are exceedingly strong nonionic bases that protonate to give the extraordinarily weak acids HP(RNCH2CH2)(3)N+ (pK(a) in MeCN, similar to 41). Thus we have found that commercially available P(MeNCH2CH2)(3)N is a superior nonionic base for the synthesis of porphyrins, alkenes, C-monoalkylation of esters and beta-hydroxy nitriles. We have also discovered that P(RNCH2CH2)(3)N cages function as superior catalysts for the synthesis of beta-hydroxy nitriles, alpha,beta-unsaturated nitriles and silyl-protected alcohols. Protective acylations of alcohols are very efficiently promoted by P(MeNCH2CH2)(3)N.