Synthesis of Atropisomeric Two‐Axis Systems by the Catalyst‐Controlled syn‐ and anti‐Selective Arene‐Forming Aldol Condensation

Simultaneous control over the configuration of multiple stereocenters is accomplished by numerous catalytic methods, providing a reliable basis for the synthesis of stereochemically complex targets in isomerically defined form. In contrast, addressing the configurations of multiple stereogenic axes with diastereodivergent catalyst control is thus far only possible by stepwise approaches. Herein we now describe that all four stereoisomers of atropisomeric two‐axis systems are directly tractable by assembling a central aromatic unit of teraryls through an arene‐forming aldol condensation. By using cinchona alkaloid‐based ion‐pairing catalysts, the four feasible reaction pathways are differentiated from identical substrates under defined basic conditions without preactivation, thus enabling complete stereodivergence with enantioselectivities of up to 99 : 1 e.r.