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

The reduction of 3-oxatricyclo[3.2.1.0^2,4]octane-endo-6-carbonitrile by lithium aluminum hydride is completed by the formation of exo-2-hydroxy-4-azatricyclo[4.2.1.0^3,7]nonane with the structure confirmed (1) by the analysis of ¹H, ¹³C, ¹⁴N, and ¹⁷O NMR spectra and the two-dimensional spectra (COSY-experiment); (2) by comparison with ¹H and ¹³C NMR spectra of the corresponding oxygen analog of heterobrendane; (3) by the calculation of the vicinal constants for the spin-spin interaction in the molecules of both analogs by the MMX program; and (4) by transformation into N-(p-bromophenylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.0^3,7]nonane prepared by an alternative synthesis, viz., epoxidation of N-(p-bromophenylsulfonyl)bicyclo-[2.2.1]hept-2-en-endo-5-methylamine. The reduction of 3-oxatricyclo [3.2.1.0^2,4]octane-exo-6-carbonitrile affords the epoxide, 3-oxatricyclo[3.2.1.0^2,4]octane-exo-6-methylamine. Different behaviors of stereoisomers are discussed; analysis of the coefficients of the atomic orbitals in the MO LCAO equation (AM1 method) has been made, and the strengths of the C(SINGLE BOND)O bonds in the epoxy ring has been analyzed. © 1997 John Wiley & Sons, Inc.