Efficient Synthesis of Aza‐triquinacene Derivatives via Cycloaddition of 2,6‐Diazasemibullvalenes with Nitroso Compounds

Abstract

The reaction between 2,6-diazasemibullvalenes and nitroso compounds was investigated. Aza-triquinacene derivatives of interesting structural and synthetic chemistry were generated highly selectively in good to excellent isolated yields. This reaction, which was rarely found between common aziridine derivatives and nitroso compounds, could be attributed to the rigid polycyclic ring system and the substitution patterns of 2,6-diazasemibullvalenes. Δ(1) -Bipyrroline derivatives were formed in excellent yields when these aza-triquinacene derivatives were treated with SmI2 .

Semibullvalene and Diazasemibullvalene: Recent Advances in the Synthesis, Reaction Chemistry, and Synthetic Applications

“…32 The reaction of NSBVs 2 with nitroso compounds cleanly afforded 2,5,8-triaza-3-oxatriquinacene derivatives 20 (Scheme 7d). 26 The normal [3 + 2] cycloaddition product was not isolated. This reaction does not require a Lewis acid catalyst.…”

“…The reactions of NSBVs with isocyanides, azides, and diazo compounds in the presence of Lewis acid catalysts represent a “ring-opening-rearrangement–cyclization” pattern. , These reactions show the most important and intriguing reactivity of NSBVs because the whole rigid-ring skeleton is involved in multisite C–C or C–N bond cleavage and formation. The use of different reagents enables efficient and selective syntheses of cage-shaped or bowl-shaped highly fused N-containing polycyclic frameworks that are structurally and chemically interesting but not readily accessible by other means.…”