Cyclisation de n-chloramines en presence d'oxyde d'argent. Synthese de molecules azapolycycliques pontees.

Azabrendanes. II. Chemo-, regio- and stereoselective transformation of 3-oxatricyclo[3.2.1.02,4]octane-endo-6-carbonitrile in reaction with lithium aluminum hydride

“…We have proposed a method for the synthesis of a precursor of the hydroxyazabrendane series, exo-2-hydroxy-4-azatricyclo[4.2.1.0 3,7 ]nonane on the basis of a practically available stereochemically homogeneous epoxy derivative, viz. bicyclo[2.2.1]hept-2-enendo-5-carbonitrile (2a).…”

“…There is no band at 850-845 cm ‫1מ‬ characteristic of epoxynorbornane in its IR spectrum [11][12][13], and there is an absorption peak in the region 3304 cm ‫1מ‬ . The signals in the NMR spectrum have been assigned using a two-dimensional spectrum (COSY-experiment) and by comparison with the spectrum of exo-2-hydroxy-4-oxatricyclo[4.2.1.0 3,7 ]nonane (7) recorded earlier [2d]. There is no resonance for the epoxy fragment protons in the region d ‫ס‬ 3 in the spectrum (Table 2).…”

“…Exo-2-hydroxy-4-azatricyclo[4.2.1.0 3,7 ]nonane (5) was prepared in a similar manner to epoxyamine (4b) via reduction of the epoxynitrile (3a) (13. Table 2; those of the 13 C NMR spectrum are given in Table 3.…”

“…N-(phenylthiocarbamoyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.0 3,7 ]nonane (11) was prepared in a similar manner to that of the urea (10) from oxyamine (5) (12). A mixture of the oxyamine (5) (1.39 g, 0.01 mol), acetic anhydride, (1.8 mL, 0.02 mol), and pyridine (4 mL, 0.05 mol) in dry chloroform (20 mL) was heated in a water bath (70ЊC).…”

“…Neuroleptic activity was studied for amides of type 1d containing a piperidine fragment in the rigid tricyclic structure [8]. Methods for regio-and stereoselective hydroxylation to yield N-substituted exo-2-hydroxy-4-azatricyclo[4.2.1.0 3,7 ]nonanes have been developed in the functionalization study of amide 1e and its analogs [8a].…”