Synthesis 1990; 1990(6): 505-508
DOI: 10.1055/s-1990-26921
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An Expedient Synthesis of Vicinal Diamines from Alkenes and Cycloalkenes

Krystyna Osowska-Pacewicka* , Andrzej Zwierzak
  • *Institute of Organic Chemistry, Technical University (Politechnika), Żwirki 36, PL-90-924 Łódź 40, Poland
Further Information

Publication History

Publication Date:
17 September 2002 (online)

A new procedure for the facile preparation of various vicinal diamines is developed that utilizes diethyl N-(β-bromoalkyl)phosphoramidates 2 easily accessible by ionic addition of diethyl N,N-dibromophosphoramidate (DBPA) to alkenes and cycloalkenes 1. Crude phosphoramidates 2 are readily transformed into the corresponding ammonium ditosylates 5 by sequential azidation, Staudinger reaction with triethyl phosphite, and deprotection by refluxing with p-toluenesulfonic acid in aqueous ethanol. Diamination of cyclohexene and indene proceeds stereospecifically affording cis-1,2-diaminocyclohexane and cis-1,2-diaminoindane, respectively. Open-chain olefins do not react stereospecifically under conventional conditions yielding mixtures of diastereoisomers. Full stereochemical control of azidation can be, however, achieved when β-bromoamine hydrochlorides instead of diethyl N-(β-bromoalkyl)phosphoramidates are used as starting materials for this reaction.