3-Benzyl-3-azabicyclo nonanes

Methylene groups adjacent to the N atom in tertiary polycyclic amines were oxidised by RuO /aq. Na(IO )/CCl, depending on reaction conditions. Thus A -benzyl-9-azabicyclo-[l, 3, 3]-nonane yielded AT-benzoyl-9-azabicyclo-[l, 3, 3]-nonane (Fig. 5.5) and A -benzyl-l,3-dioxo-iso-quinoline gave the A -benzoyl compound, while A -benzyl-5,6-dihydro-llH-dibenz[b,e]azepine, which has exi and endocydic benzyl groups, were oxidised to the N-benzyl-6-oxo derivative [41]. 

The exo-2-methyl- and ethyl-substituted 3-benzyl-3-azabicyclo[3.3.1]-nonanes were shown to adopt the CC conformation in solution (from 13C-NMR data), while for the exo-2-isopropyl compound the CB conformation is predominant (106). 

S,6R,9S)-7-Benzyl-9-hydroxy-7-azabicyclo[4.2.1]nonane-4,8-dione 2. A solution of 1 (3.19 g, 11.1 mmol) in HCOOH (55 mL) was stirred at 85°C for 2.5 days. The residue obtained after evaporation in vacuum was stirred for 1 h at 20°C in 50% methanolic NH3 (50 mL). After evaporation of the MeOH the residue was chromatographed (CH2CI2 Me2CO 1 1) to give 2. Recrystallization from EtOAc afforded... 

It , 61 , 91 )- and (lJ , 6J , 9Sw)-8-Benzyl-4-etliyl-5-mctliyl-9-phenyl-3,7-dioxa-8-azabicyclo 4.3,0 nonan-2-one93 ... 

A-Benzyl-3-azabicyclo[3.1.0]hexan-l-ols, which are readily available from a Kulinkovich reaction, are converted by CAN into benzaimulated l-azabicyclo[3.3.1]-nonan-3-ones. ° This oxidation pathway differs from that mediated by FeCls. 

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