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1‐Vinyltricyclo[4.1.0.0 2,7 ]heptanes: Synthesis and Reactions with Electrophilic Dienophiles
Author(s) -
Kreuzholz Rüdiger,
SchmidVogt Wolfgang,
Maierhofer Monika,
Polborn Kurt,
Stephenson David S.,
Szeimies Günter
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199801)1998:1<29::aid-ejoc29>3.0.co;2-q
Subject(s) - chemistry , electrophile , tetracyanoethylene , dimethyl acetylenedicarboxylate , carbenium ion , zwitterion , medicinal chemistry , ionic bonding , double bond , cycloaddition , catalysis , organic chemistry , ion , molecule
A series of 1‐vinyltricyclo[4.1.0.0 2,7 ]heptanes 4 has been obtained by Ni 0 ‐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 .