Iron-Catalyzed Ring-Opening of meso-Aziridines with Amines

Abstract

A cationic iron complex has been found to catalyze the aminolysis of meso-N-aryl aziridines very efficiently furnishing valuable 1,2-diamines in typically excellent yields. This protocol is compatible with a range of functional groups both in the aziridine and amine components.

amine - aziridine - catalysis - 1,2-diamine - iron

References and Notes

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3n

See ref. 9.

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8a

Ligand: mep = N,N-dimethyl-N,N-bis(2-pyridylmethyl)-ethane-1,2-diamine; BPMEN is another commonly employed abbreviation for this ligand.

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9 For a highly enantioselective Ti-catalyzed ring-opening of meso-aziridines with amines, see: Peruncheralathan S. Teller H. Schneider C. Angew. Chem. Int. Ed.  2009,  48:  4849 

For scandium- and indium-catalyzed ring-opening reactions of aziridines, see:

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Silver salts are known to be capable of abstracting chloride anions of transition-metal complexes resulting in cationic metal complexes, see e.g.:

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12

General Procedure for the Iron-Catalyzed Ring-Opening of meso -Aziridines with Amines
FeCl₂(mep) (24 mg, 0.05 mmol, 5 mol%) was dissolved in CH₂Cl₂ (2 mL) and mixed with AgSbF₆ (34 mg, 0.10 mmol, 10 mol%), under an argon atmosphere, for 30 min at r.t. Subsequently, a solution of the aniline (1.20 mmol) in CH₂Cl₂ (1 mL) was added followed by a solution of the respective aziridine (1.00 mmol) in CH₂Cl₂ (1 mL). Stirring was continued at r.t. until the reaction was judged complete by GC analysis. The GC yields were determined against iodobenzene as internal standard. The solvents were removed under nitrogen flux, and the crude product was purified with chromatography over silica gel using pentane-EtOAc (30:1) as eluent. For analytical and spectroscopic details of the products, see ref. 3.