Reactions of Vinylidenecyclopropanes with Diphenyl Diselenide in the Presence of AIBN and Thermally‐Induced Further Transformations

Abstract

Radical transformers: The chemical transformation of vinylidenecyclopropanes with diphenyl diselenide in the presence of AIBN and upon heating gives the corresponding bicyclo[3.1.0]hexane derivatives in good yields. These compounds undergo thermal‐induced radical 1,4‐hydrogen shifts through a ring‐opening pathway of allylic cyclopropane to give the corresponding cyclohexene derivatives stereoselectively in good yields at 200 °C (see scheme).

1,n‐Hydrogen‐Atom Transfer (HAT) Reactions in Which n≠5: An Updated Inventory

“…Vinylidene cyclopropanes of type 17.2 are available in high yield through radical addition of diphenyl diselenide to allenylcyclopropanes 17.1 (Scheme ) 46. The involvement of 1,4‐HAT in the thermal rearrangement of vinylbicyclo[3.1.0]hexanes was demonstrated by isotopic labeling.…”

“…Vinylidene cyclopropanes of type 17.2 are available in high yield through radical addition of diphenyl diselenide to allenylcyclopropanes 17.1 (Scheme 17). [46] The involvement of 1,4-HAT in the thermal rearrangement of vinylbicyclo-[3.1.0]hexanes was demonstrated by isotopic labeling. As exemplified with the labeled compound, 1,4-deuterium atom transfer occurring in the preferred conformer 17.4 of the biradical intermediate could rationalize the high yielding synthesis of 17.6.…”

Studien zur oxidativen Funktionalisierung von Alkenen mittels Selen-pi-Säure-Katalyse

“…Darüber hinaus gelang die Selenofunktionalisierung von Alkinen ebenfalls unter Verwendung photochemisch generierter Selenelektrophile. [396,397] Die oxidative Freisetzung des korrespondierenden Allens aus den erhaltenen Vinylseleniden ist jedoch nur für wenige Fälle bekannt, [398][399][400] und eine selenkatalysierte Variante, die beide Teilprozesse in einem Reaktionsschritt vereint, wurde bis heute nicht berichtet.…”