Catalyst-free formal [4+1]/[4+2] cyclization cascade sequence of isocyanides with two molecules of acylketene formed in situ from thermal-induced Wolff rearrangement of 2-diazo-1,3-diketones.

An expedient and economic approach for constructing O,O,N-spiro compounds consisting of both a 1,3-oxazine and a furan ring through a catalyst-free formal [4+1]/[4+2] cycloaddition cascade sequence of isocyanides with two molecules of acylketene formed in situ through thermal-induced Wolff rearrangement of 2-diazo-1,3-diketones was developed. The reaction displayed good functional group tolerance and was compatible with different isocyanides and 2-diazo-1,3-diketones. Furthermore, preliminary asymmetric attempts of this reaction are made by utilizing optically pure isocyanides as inputs, and moderate diastereomeric induction was observed.