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Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes
Author(s) -
Hayashi Mikayo,
Brown Lauren E.,
Porco John A.
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201601003
Subject(s) - chemistry , ligand (biochemistry) , chemotype , enantioselective synthesis , palladium , bicyclic molecule , combinatorial chemistry , stereochemistry , organic chemistry , catalysis , receptor , biochemistry , chromatography , essential oil
Enantioenriched, polycyclic compounds were obtained from a simple acylphloroglucinol scaffold. Highly enantioselective dearomatization was accomplished using a Trost ligand–palladium(0) complex. A computational DFT model was developed to rationalize observed enantioselectivities and revealed a key reactant‐ligand hydrogen bonding interaction. Dearomatized products were used in visible light‐mediated photocycloadditions and oxidative free radical cyclizations to obtain novel polycyclic chemotypes including tricyclo[4.3.1.0 1,4 ]decan‐10‐ones, bicyclo[3.2.1]octan‐8‐ones and highly substituted cycloheptanones.