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

ABSTRACT: 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 ?-hydroxy amines, a common structural motif of biologically active compounds.

SUBMITTER: Trost BM

PROVIDER: S-EPMC5726861 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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

Trost Barry M BM Tracy Jacob S JS

Organic letters 20170503 10

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 β-hydroxy amines, a common structural motif of biologi ...[more]

PMID: 28467706

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