Behaviour of the gem-cyano-ethoxycarbonyl cyclohexane, thiopyran and pyran derivatives with sodium borohydride and lithium aluminium hydride

Article abstract of DOI:10.1016/S0040-4020(01)87766-8

Treatment of the gem-cyano ethoxycarbonyl compounds 1a-c with NaBH4 in 2-propanol or PEG-400 produced reduction of the ethoxycarbonyl group and simultaneous reductive deacetoxylation.Similar treatment of 7 with NaBH4-CoCl2 produced selective reduction of the cyano group to aminomethyl group and rearrangement O->N of an acetyl group to aminomethyl group.Treatment of 1a-c and 7 with LiAlH4 gave, after acetylation, the gem-aminomethyl-hydroxymethyl compounds 6a-c and 11 respectively.Compounds 4a-b, 5a-b and 6a-b show a prefered conformation with both acetoxy groups in an equatorial disposition.However compounds 4c, 5c and 6c prefer the conformation with both acetoxy groups in an axial disposition.