Azaphosphatrane Cations: Weak Acids, Robust Phase‐transfer Catalysts

The use of azaphosphatrane derivatives, which are the acidic counterparts of the well‐known proazaphosphatrane superbases (also named Verkade’s superbases), are found to function as phase‐transfer catalysts. In four representative protocols of phase‐transfer catalytic reactions—two alkylations of enolates, one generation of carbene, and one oxidation of an electrophilic alkene—azaphosphatranes act as catalysts in biphasic heterogeneous media.