Stereoselective Synthesis of 3,4,5,6-Tetrasubstituted (1R,2R)-Diaminocyclo­hexanes by Zirconium-Promoted Reductive Cyclisation

Abstract

The reactions of η²-(1-butene)zirconocene with (4R,5R)-di[(1S)-phenylethyl]amino-1,7-octadienes, carrying two vinyl or two phenyl substituents at C3 and C6, followed by protonation, gave a mixture of diastereomeric, fully substituted cyclohexanes. In the case of (4R,5R)-di[(1S)-phenylethyl]amino-(3R,6R)-diphenyl-1,7-octadiene, the main diastereomer of the product was isolated with 41% yield, then reductive removal of the N-substituents afforded (1R,2R)-diamino-(4R,5S)-dimethyl-(3R,6R)-diphenylcyclohexane with 91% yield.

Key words

alkenes - amines - chiral auxiliaries - asymmetric synthesis - cyclisations - zirconium

References

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Supporting information available: ¹H NMR spectra assignments for 5a, b and 7a; COSY 45 and NOESY spectra of the aliphatic regions of 5a, b and COSY sprectra of the aliphatic region of 7a.