7076-81-5Relevant articles and documents
Probing the nature and extent of stabilization within foiled carbenes: Homoallylic participation by a neighboring cyclopropane ring
Apeland, Ingrid Malene,K?hlig, Hanspeter,Lorbeer, Eberhard,Brinker, Udo H.
, p. 4879 - 4885 (2013/07/11)
Oxadiazoline 6 was synthesized to generate endo-tricyclo[3.2.1.0 2,4]octan-8-ylidene (3) by either photolysis or thermolysis. Diastereomer 6a thermally decomposed twice as fast as 6b. Carbene 3 was trapped stereoselectively by acrylonitrile and diethylamine in high yields. It behaved as a nucleophilic carbene with electron-poor alkenes, like acrylonitrile, but as an electrophile with very electron-rich species, such as diethylamine. However, when the reactions were performed in cyclohexane and cyclohexene, isomerization of 3 was favored. Replacement of the double bond in 7-norbornenylidene (1) by the single bond in the endo-fused cyclopropane unit of carbene 3 led to similar outcomes. Carbene 3 rightfully belongs to the family of foiled carbenes.
