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

Azabrendanes V. Synthesis and reactions of stereoisomeric exo- and endo-5-aminomethylbicyclo[2.2.1]hept-2-ene-based ureas

“…Compound 31 has been previously obtained from azabrendane parent compound 38 , by chemo-, regio-, and stereoselective reduction of endo-5-cyano-exo-2,3-epoxybicyclo[2.2.1]heptane (Scheme 9) [31].…”

The (±)-5-Aza[1.0]triblattane Skeleton via Azetine Cycloaddition

“…10 In light of the precedence of N-acetyl-2-azetine (10) undergoing [4 + 2] cycloaddition with cyclopentadiene (9), 8 the synthesis of 10 was therefore pursued. Following the optimized procedure of Engelsma et al, 10 synthesis of the azetidine mesylate (11) was started by reaction of epichlorohydrin (12) with benzhydrylamine (13) to provide the azetidinol 14 in 56% yield. 11 Conversion of alcohol 14 to the corresponding mesylate (i.e., 15) with methanesulfonyl chloride was followed by dealkylation using α-chloroethyl chloroformate (16) to give desired hydrochloride salt 11 in 78% yield (Scheme 2).…”

“…The corresponding cycloadducts were obtained in good yields (Table 2). 13 1 H and 13 C NMR spectroscopy suggested only the endo-isomer was produced (i.e., 21) but as a mixture of rotamers on the NMR time scale.…”

“…Treatment of 7 with sodium hypochlorite provided the N-chloroalkene 22 with high purity. Initially, exposure of 22 to excess TFA in deuterated chloroform (CDCl 3 ) gave 23, 13 together with the reduced product 7. Crystalline material of 23 could be obtained, which enabled X-ray crystallographic confirmation of the structure (Scheme 3).…”