Carbon-Nitrogen Bond Formation via the Vanadium Oxo Catalyzed Sigmatropic Functionalization of Allenols.

A vanadium catalyzed 1,3-rearrangement of allenols to form transient vanadium enolates that selectively couple with electrophilic nitrogen sources is reported even in the presence of competing simple protonation and Alder-ene pathways. Hydrazine products can be cyclized in a 6-endo-trig fashion which, upon reductive cleavage of the N-N bond, yield 1,4-diamines. Additionally, cleavage of the N-N bond before cyclization can be achieved to form ß-hydroxy amines, a common structural motif of biologically active compounds.