Highly Enantiomerically Enriched Planar Chiral Naphthalene Tricarbonylchromium Complexes

Lithiation/electrophile trapping reactions were carried out with the highly enantiomerically enriched complex [Cr(5‐bromonaphthalene)(CO)₃]. Electrophile quenching with ClPPh₂, PhCHO, and (Me₃SiO)₂ afforded the enantiomerically enriched (>97 % ee) planar chiral 5‐substituted naphthalene complexes with PPh₂, CH(Ph)OH, and OH substituents, respectively. Very mild Pd‐catalyzed Suzuki–Miyaura cross‐coupling reactions were developed and applied to the highly labile [Cr(5‐bromonaphthalene)(CO)₃] to give nine new planar chiral aryl‐, heteroaryl‐, alkynyl‐, and alkenylnaphthalene chromium complexes with high enantiomeric purity. The efficient ambient‐temperature coupling reactions with borinates prepared in situ were also applied to a number of chlorobenzene complexes and to aryl and vinyl halides.