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Cobalt‐Catalyzed ortho ‐C−H Functionalization/Alkyne Annulation of Benzylamine Derivatives: Access to Dihydroisoquinolines
Author(s) -
Martínez Ángel Manu,
Rodríguez Nuria,
GómezArrayás Ramón,
Carretero Juan C.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702283
Subject(s) - benzylamine , annulation , alkyne , chemistry , surface modification , combinatorial chemistry , catalysis , reagent , medicinal chemistry , organic chemistry
Abstract A practical picolinamide‐directed C−H functionalization/alkyne annulation of benzylamine derivatives enabling access to the previously elusive 1,4‐dihydroisoquinoline skeleton was developed using molecular O 2 as the sole oxidant and Co(OAc) 2 as precatalyst. The method is compatible with both internal and terminal alkynes and shows high versatility and functional‐group tolerance. Furthermore, full preservation of enantiopurity is observed when using non‐racemic α‐substituted benzylamine derivatives. Kinetic analysis of the reagents and catalyst, labeling experiments, and the isolation and identification of catalytically competent Co‐complexes revealed important insights about the mechanism.