Enantioselective Dearomative Difunctionalization of Indoles by Palladium‐Catalyzed Heck/Sonogashira Sequence

• Published in: Angewandte Chemie International Edition Vol. 56; no. 26; pp. 7475 - 7478
• Main Authors: Liu, Ren‐Rong, Wang, Yong‐Gang, Li, Ying‐Long, Huang, Bing‐Bing, Liang, Ren‐Xiao, Jia, Yi‐Xia
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 19.06.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: alkynes; asymmetric catalysis; Chemistry; Chemistry, Multidisciplinary; dearomatization; Enantiomers; heterocycles; Heterocyclic compounds; Indoles; Palladium; Physical Sciences; Science & Technology; HALIDES; ARYLATIVE DEAROMATIZATION; DOMINO PROCESSES; alkynes; dearomatization; ASYMMETRIC HECK REACTION; asymmetric catalysis; INTRAMOLECULAR DEAROMATIZATION; REDUCTIVE ELIMINATION; heterocycles; CYCLIZATION-ANION CAPTURE; CONSTRUCTION; palladium; DERIVATIVES; EFFICIENT
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201703833

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) and diastereoselectivities (>20:1). Double the function: A highly enantioselective dearomative arylalkynylation of N‐substituted indoles with alkynes has been established by using palladium and a BINOL‐based phosphoramidite as the chiral ligand. A wide range of 2,3‐disubstituted indolines, bearing vicinal tertiary and quaternary stereocenters, were constructed in one step with excellent enantio‐ and diastereoselectivities.