Crossed Regio‐ and Enantioselective Iron‐Catalyzed [4+2]‐Cycloadditions of Unactivated Dienes

The cyclohexene motif is ubiquitous in nature and specialty chemicals. A straightforward selective access to chiral cyclohexenes from unactivated dienes and dienophiles is not feasible by classical Diels–Alder reaction and constitutes an unsolved synthetic challenge. We report a mild and enantioselective iron‐catalyzed cross‐[4+2]‐cycloaddition of unactivated dienes providing access to chiral 1,3‐substituted vinyl‐cyclohexenes. The development of bis‐dihydroisoquinoline ligands was vital to obtain iron complexes that display high reactivities and excellent chemo‐, regio‐ and enantioselectivities towards the targeted cyclohexenes. A range of diene substrates is well accommodated including feedstocks like butadiene, isoprene and myrcene. The structures of different iron complexes are mapped by X‐ray crystallographic analysis and linked to their performance.