A tandem reaction strategy for forming triquinanes from linear allenyl diazo compounds through an intramolecular 1,3-dipolar cycloaddition reaction of an allenyl diazo group that generates a trimethylenemethane (TMM) diyl followed by an intramolecular [2 + 3] TMM diyl cycloaddition reaction has been developed. The new tandem cycloaddition reaction is readily applicable to the synthesis of complex molecules with high versatility and efficiency.
Total synthesis of ceratopicanol (1) was achieved with a tandem cycloaddition reaction of allenyl diazo compound 6 via a trimethylenemethane (TMM) diyl intermediate. The TMM diyl mediated [2+3] cycloaddition reaction furnished the consecutive quaternary carbon centers and showed an unusual diastereoselectivity.
trans‐Fused triquinane: Intramolecular‐trimethylenemethane‐mediated [2+3] cycloaddition reaction of a highly congested substrate proceeded stepwise to produce highly strained triquinane structures along with tricyclo[5.3.1.02, 6]undecanes.
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