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Rh(III)-Catalyzed Oxidative [5 + 2] Annulation Using Two Transient Assisting Groups: Stereospecific Assembly of
Wei Yi1, Liping Li1, Hongzhen Chen1
1Key Laboratory of Molecular Target & Clinical Pharmacology and the State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences & the Fifth Affiliated Hospital , Guangzhou Medical University , Guangzhou , Guangdong 511436 , China.
Abstract:
A unique Rh(III)-catalyzed oxidative [5 + 2] annulation of easily available 2-alkenylphenols with propargyl carbonates have been developed by using two O-containing functional groups as the traceless assisting groups (AGs). The experimental investigations together with the density functional theory (DFT) calculations revealed that this transformation involves the free OH-directed cleavage of one terminal C-H bond of the alkenyl moiety and regioselective alkyne insertion, followed by OBoc-promoted intramolecular nucleophilic substitution and β-H elimination that used an allyl species as the active intermediate, giving direct access to the 3-alkenylated benzoxepine skeleton with broad substrate compatibility and good functional group tolerance.
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