Hydrogen Bond Direction Enables Palladium-Catalyzed Branch- and Enantioselective Allylic Aminations and Beyond

The palladium-catalyzed
branch- and enantioselective allylic amination
of vinyl benzoxazinones was accomplished through controlling the hydrogen
bond direction. This protocol provides a rapid and efficient route
for synthesizing an important building block, chiral amino alkene,
from widely available aliphatic amines in 64 → 99% yields with
up to 99% ee. Furthermore, this transformation and the accompanying
products were utilized to develop one-pot reactions through dual catalysis,
affording chiral indolines with good synthetic efficiency and excellent
enantiocontrol.