上海科技大学知识管理系统

Axially chiral diarylamine atropisomers represent a distinct category characterized by two contiguous chiral C-N axes, which exhibit a significantly lower racemization barrier due to the concerted rotation of both C-N axes. In this work, we introduce an effective method for the atroposelective synthesis of axially chiral diarylamines through organocatalyzed asymmetric electrophilic amination with azodicarboxylates, which afforded a variety of acyclic secondary diarylamine atropisomers in good yields with high enantioselectivities. This method expands the scope of catalytic asymmetric synthesis beyond N-aryl quinoid-type atropisomers, enabling the catalytic atroposelective synthesis of chiral diarylamines without constraining one C-N axis through intramolecular hydrogen bonding. Both experimental and computational studies show a minimal contribution of intramolecular hydrogen bonding in stabilizing configurations of these atropisomers, which undergo racemization via the concerted rotation of both C-N axes. © 2024 American Chemical Society.