ISSN:
1434-193X
Keywords:
Strained molecules
;
1-Vinyltricyclo[4.1.0.02,7]heptanes
;
Electrophilic additions
;
Rearrangements
;
Cyclic ketene imine
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A series of 1-vinyltricyclo[4.1.0.02,7]heptanes 4 has been obtained by Ni0-catalyzed cross-coupling reactions of the corresponding Grignard reagent with vinyl halides or via reaction of 4b with various electrophiles. Selected model compounds 4 were treated with tetracyanoethylene (TCNE), N-phenyl-1,2,4-triazoline-3,5-dione (PTAD), and dimethyl acetylenedicarboxylate (DMAD). Product studies revealed that TCNE and PTAD attacked the CC double bond forming a zwitterion, which in most cases underwent several carbenium ion rearrangements until internal bond formation of the ionic centers took place. The main reaction path of DMAD and 4 led via attack at the bicyclo[1.1.0]butane bridgehead to a biradical of type 38, which after H abstraction and CC bond formation gave rise to the tricyclic system 37.
Type of Medium:
Electronic Resource
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