Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes

作者：Hayashi Mikayo; Brown Lauren E^*; Porco John A Jr^*

来源：European Journal of Organic Chemistry, 2016, 2016(28): 4800-4804.

DOI：10.1002/ejoc.201601003

• Asymmetric catalysis
• Dearomatization
• Photocatalysis
• Radical reactions
• Polycycles

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.

• 出版日期2016-10