Organocatalytic Higher-Order [8+2] Cycloaddition for the Assembly of Atropoenantiomeric 3-Arylindolizines.

We present an unprecedented atroposelective [8+2] cycloaddition reaction between pyridinium/isoquinolinium ylides and ynals. It is worth noting that this protocol represents a new example of the organocatalyzed atropoenantioselective higher-order cycloaddition reaction, providing various axial chiral 3-arylindolizines in good yields and high enantioselectivities. In addition, the obtained axially chiral 3-aryldolizines also provide many opportunities for structural transformations and potential drug discovery.