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anti ‐Dioxylation of Cyclohex‐4‐ene‐1,2‐diamine Derivatives: Asymmetric Routes to Hydroxy‐ and Amino‐Substituted Cyclohexane and 7‐Azanorbornane
Author(s) -
Savoia Diego,
Balestri Davide,
Grilli Stefano,
Monari Magda
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201301700
Subject(s) - chemistry , epoxide , diamine , stereoselectivity , protonation , medicinal chemistry , cyclohexene , diol , cyclohexane , double bond , ring (chemistry) , stereochemistry , ene reaction , sulfonate , organic chemistry , catalysis , ion , sodium
The highly diastereoselective anti ‐dioxylation of (1 R ,2 R )‐1,2‐bis[(1 S )‐phenylethylamino]cyclohexene was accomplished through epoxidation of the double bond with m ‐chloroperbenzoic acid ( m CPBA) in the presence of a sulfonic or trihaloacetic acid and ring opening of the epoxide in situ in the presence of sulfonate or carboxylate anions. The two procedures, after basic quenching and reductive removal of the N‐substituents, provide stereoselective access to 2‐ exo ‐5‐ endo ‐5‐amino‐7‐azabicyclo[2.2.1]heptan‐2‐ol and 4,5‐diaminocyclohexane‐1,2‐diol, respectively. The different outcomes are explained by differing chair conformations of the protonated diamine‐epoxide intermediates, which undergo ring opening through a preferred anti ‐diaxial mechanism.