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

Citation
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
Citations number
58
Categorie Soggetti
Chemistry & Analysis","Organic Chemistry/Polymer Science
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1
ISSN journal
0300922X → ACNP
Volume
9
Year of publication
2000
Pages
1351 - 1361
Database
ISI
SICI code
0300-922X(2000)9:<1351:AAONAE>2.0.ZU;2-K
Abstract
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.