J. Clayden et al., Atroposelective attack of nucleophiles and electrophiles on 2-acyl-1-naphthamides and their enolates, J CHEM S P1, 9, 2000, pp. 1351-1361
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.