Gold-Catalyzed Bicyclic and [3+2]-Annulations of Internal Propargyl Alcohols with Nitrones and Imines To Yield to Two Distinct Heterocycles

A gold-catalyzed synthesis of 1,3-dihydrooxazolo[3,4-a]indoles from 1-oxo-3-yn-4-ols and nitrones is described; this new bicyclic annulation presents the first examples that internal alkynes can react with nitrones to undergo an oxoarylation route. DFT calculations indicate a [3,3]-sigmatropic shift of initial alkenylgold intermediates to elude the intermediacy of gold carbenes. We also developed new [3+2]-annulations of the same 1-oxo-3-yn-4-ols with imines, yielding oxazolidin-4-ylidene derivatives efficiently. The tethered alcohols of these 1-oxo-3-ynes allow trapping of their metastable 2-azadienium intermediates to enable a novel annulation. Our mechanistic analysis indicates that the two products, despite their structural relevance, are produced from two independent systems.

Automated summary

A gold-catalyzed synthesis method for 1,3-dihydrooxazolo[3,4-a]indoles from 1-oxo-3-yn-4-ols and nitrones is described. The research demonstrates that internal alkynes can undergo oxoarylation reaction with nitrones, revealing the underlying chemical mechanism.