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Palladium‐catalyzed enantioselective dearomative arylalkynylation of N‐substituted indoles, through a Heck/Sonogashira sequence, was established using a new BINOL‐based phosphoramidite as the chiral ligand. A wide range of 2,3‐disubstituted indolines, bearing vicinal quaternary and tertiary stereocenters, were efficiently constructed in one step with excellent enantioselectivities (up to 97 % ee)...
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