Atroposelective Synthesis of 1,1′‐Bipyrroles Bearing a Chiral N−N Axis: Chiral Phosphoric Acid Catalysis with Lewis Acid Induced Enantiodivergence

Abstract We present herein a highly efficient atroposelective synthesis of axially chiral 1,1′‐bipyrroles bearing an N−N linkage from simple hydrazine and 1,4‐diones. Further product derivatizations led to axially chiral bifunctional compounds with high potential in asymmetric catalysis. For this chrial phosphoric acid (CPA)‐catalyzed double Paal–Knorr reaction, an intriguing Fe(OTf) 3 ‐induced enantiodivergence was also observed.