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One-Pot Preparation of 9,10-Dihydrophenanthrenes Initiated by Rhodium(III)-Catalyzed C–H Activation and Relay Diels–Alder Reaction

Dingding Gao, Xingyu Liu, Hao Xu, Yun‐Xuan Tan, Qi Liao, Qinghua Li, Xiaodi Yang, Guo‐Qiang Lin, Ping Tian

2020Organic Letters14 citationsDOI

Abstract

An efficient one-pot synthesis of multisubstituted 9,10-dihydrophenanthrenes from easily available 2-arylazaarenes and cyclohexadienone-tethered terminal alkynes (1,6-enynes) has been successfully achieved. This domino reaction proceeded smoothly through Cp*Rh(III)-catalyzed C-H activation, direct protonation of alkenyl-Rh intermediates, intramolecular Diels-Alder reaction, alkene isomerization, subsequent ring-opening aromatization, and acetylation. This strategy was pot-economical and tolerated a wide range of functional groups. Moreover, the potent anticancer activities against HepG2 cells were observed for these artificial 9,10-dihydrophenanthrene derivatives.

Topics & Concepts

ChemistryAromatizationIntramolecular forceRhodiumCatalysisIsomerizationDiels–Alder reactionProtonationAlkeneMedicinal chemistryCombinatorial chemistryCycloisomerizationStereochemistryOrganic chemistryIonCatalytic C–H Functionalization MethodsCatalytic Alkyne ReactionsCyclopropane Reaction Mechanisms