Atroposelective attack of nucleophiles and electrophiles on 2-acyl-1-naphthamides and their enolates

Organolithiums, Grignard reagents and borohydride reducing agents attack 2- acyl-1-naphthamides to give tertiary and secondary alcohols with high or co mplete atroposelectivity. High levels of stereoselectivity can also be obta ined in the alkylations of enolates derived from the same ketones, though t he low barrier to thermal epimerisation of the product ketones prevents acc urate determination of the kinetic stereoselectivity of the alkylation. The direction of attack in both cases is controlled by the perpendicular confo rmation of the aromatic amide substituent, whose NR2 group shields one face of the ketone.