title: Relaying asymmetry of transient atropisomers of o-iodoanilides by radical cyclizations.
abstract: Atropisomers of N-2 degrees -alkyl-N-acryloyl-2-iodoanlides have been resolved by chromatography and crystallization-induced asymmetric transformation. These molecules have atropisomerization barriers of 23-24 kcal/mol and return to equilibrium ratios over several hours at ambient temperature in solution. The transient chirality can be locked in by radical cyclizations, which provide N-2 degrees -alkyl-3-methyl-1,3-dihydroindol-2-ones with high levels of chirality transfer. The mechanistic model features a stereoselective aryl radical cyclization that is more rapid than the rotation of the N-aryl bond of the anilide.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Marc
authors.initials: M
authors.lastname: Petit
authors.forename: Andre J B
authors.initials: AJ
authors.lastname: Lapierre
authors.forename: Dennis P
authors.initials: DP
authors.lastname: Curran